The stability of annite+quartz: reversed experimental data for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite +2 H2O

Reversals for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite+2 H₂O have been experimentally determined in cold-seal pressure vessels at pressures of 2, 3, 4 and 5?kbar, limiting annite +quartz stability towards higher temperatures. The equilibrium passes through the temperature intervals 500–540°?C (2?kbar), 550–570°?C (3?kbar), 570–590°?C (4?kbar) and 590–610°?C (5?kbar). Starting materials for most experiments were mixtures of synthetic annite +fayalite+sanidine+quartz and in some runs annite+quartz alone. Microprobe analyses of the reacted mixtures showed that the annites deviate slightly from their ideal Si/Al ratio (Si per formula unit ranges between 2.85 and 2.92, Al^VI between 0.06 and 0.15). As determined by Mössbauer spectroscopy, the Fe³⁺ content of annite in the assemblage annite+fayalite +sanidine+quartz is around 5–7%. The experimental data were used to extract the thermodynamic standard state enthalpy and entropy of annite as follows: H ⁰ _f,?Ann =?5125.896±8.319 [kJ/mol] and S ⁰ _Ann=432.62±8.89 [J/mol/K] (consistent with the Holland and Powell 1990 data set), and H ⁰ _f,Ann =?5130.971±7.939 [kJ/mol] and S ⁰ _Ann=424.02±8.39 [J/mol/K] (consistent with the TWEEQ data base, Berman 1991). The preceeding values are close to the standard state properties derived from hydrogen sensor data of the redox reaction annite=sanidine+magnetite+H ₂ (Dachs 1994). The experimental half-reversal of Eugster and Wones (1962) on the annite +quartz breakdown reaction could not be reproduced experimentally (formation of annite from sanidine+fayalite+quartz at 540°?C/1.035?kbar/magnetite-iron buffer) and probable reasons for this discrepancy remain unclear. The extracted thermodynamic standard state properties of annite were used to calculate annite and annite+quartz stabilities for pressures between 2 and 5?kbar.     

Ore-forming solution and genesis of a rock crystal deposit in south Hunan,indicated by fluid inclusion studies

Si, Al, Ca, Mg, Fe, Na, K, CO ₃ ^?2 , F, etc. are detected from the fluid inclusion leachates. Among these constituents, Si, Na, and CO ₃ ^?2 are predominant, amounting to more than 80 percent. This indicates that the ore-forming solution must be alkaline with Si, Na, and CO ₃ ^?2 as its dominant components. Homogenization temperatures for the solution range from 80 to 360°C. Although rock quartz can crystallize at the above temperature interval, perfect crystals of economic importance are largely formed below 260°C. The temperature of formation increases toward the granite intrusives at a rate of about one degree per meter. It is estimated from the lithostatic load that the salinity of rock quartz is 17–23 (NaCl wt%), while that of vein quartz is relatively high as compared with the former. There is a tendency for the salinity of the ore-forming solution to increase with depth.     

Experimental determination of portlandite and brucite solubilities in supercritical H2O

Experimentally reversed portlandite and brucite solubilities were determined between 300° and 600°C and 1 to 3 kbar. In the portlandite runs the molality of Ca decreases with increasing pressure at constant temperature. For instance, at 2 kbar log molalities at 300°, 400°, 500° and 600°C give values of −2.34, −2.71, −3.18 and −4.18, respectively. At 500°C, pressures of 1, 2 and 3 kbar yield values of −4.40, −3.18 and −2.65. Distribution of species in solution can be calculated with the aid of data from Helgeson and co-workers assuming Ca⁺⁺ is the dominant Ca species. These calculated Ca concentrations are within ± 0.2 log units of experimental values in most cases. The solubility reaction is, in all likelihood: 2H⁺ + Ca(OH)₂ ↔a3 Ca⁺⁺ + 2H₂O.Although the computed pH's are close to 2 units greater than neutral, the solutions apparently contained no significant Ca(OH)⁺ or Ca(OH)_2sq.Concentrations of Mg in the brucite runs show a sigmoidal behavior at 2 kbar as a function of temperature with log molalities of Mg of −4.00, −4.28, −4.14 and −4.60 at 350°, 450°, 550° and 600°C, respectively. Values at 1 kbar are lower and decrease monotonically from 350° to 550°C. Based on available thermodynamic data for Mg⁺⁺ it appears that Mg(OH)⁺ is the dominant Mg species in solution. The solubility reaction is proposed to be: H⁺ + Mg(OH)₂↔a3 Mg(OH)⁺ + H₂O.With the aid of data of Helgeson and co-workers values of the equilibrium constant for H₂O + Mg⁺⁺ ↔a3 Mg(OH)⁺ + H⁺ necessary to account for the measured solution compositions can be calculated. These calculations indicate Mg(OH)⁺ becomes dominant at temperatures above 450°C at 2 kbar and above 360°C at 1 kbar at neutral pH.     

Ion exchange between tectosilicates with the nepheline-kalsilite framework and molten MNO3 or MO (M = Li,Na, K,Ag)

Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO₃ or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K_0.3,□)Li₃[Al₃(Al,Si)Si₄O₁₆] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag₃[Al₃(Al,Si)Si₄O₁₆] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na₃[Al₃(Al,Si)Si₄O₁₆] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na₃[Al₃(Al,Si)Si₄O₁₆], but not with the potassian end member (K,□)₄[Al₃(Al,Si)Si₄O₁₆] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).     

Determination of the first ionization constant of silicic acid from quartz solubility in borate buffer solutions to 350°C

The solubility of quartz has been determined in borax buffer solutions having total boron concentrations of 0.10, 0.20, 0.40 and 0.60 mol kg^?1 and over the temperature range 130–350°C at the saturated vapour pressure of the system. The first ionization constant of silicic acid was calculated from the solubility data and varied from ?logK₁ = 8.88 (± 0.15) at 130°C to ?logK₁ = 10.06 (± 0.20) at 350°C. The solubility of quartz in these solutions was due to the presence of the three species, H₄SiO₄, H₃SiO₄^? and NaH₃SiO₄°. The equilibrium constant for the reaction, Na⁺ + H₃SiO₄^? = NaH₃SiO₄° extended from log K_as = 1.18?1.40 (± 0.20) over the temperature interval 135–301°C. The formation of NaH₃SiO₄° ion pairs was concluded to contribute significantly to the solubility of quartz in alkaline hydrothermal solutions when pH > 8 and sodium concentration exceeds 0.10 mol kg^?1.     

Geothermobarometry on anatectic melts – a high-pressure Variscan migmatite from northeast Sardinia

We studied a high-pressure amphibole-bearing migmatite cropping out along the northeastern coast of Sardinia, a few kilometres northeast of Olbia, in order to improve our knowledge about its evolution using pressure–temperature (P–T) pseudosections. Thermodynamic calculations with PERPLE_X were undertaken in the system Na₂O–K₂O–CaO–FeO–MnO–MgO–Al₂O₃–TiO₂–SiO₂–H₂O using a haplogranitic melt model. Calculations were conducted for average compositions of the protolith and the tonalitic leucosome with different contents of H₂O to construct various pseudosections in the P–T range 2–20 kbar and 550–900°C. We demonstrate that the molar ratios Na/K and Si/Al of the anatectic melt are of high geothermobarometric value. Particularly the melt field in the P–T pseudosection for the protolith, contoured by Si/Al isolines, shows a significant decrease in this ratio with rising pressure. This ratio is only weakly dependent on variable H₂O contents of the amphibole-bearing migmatite as demonstrated by contoured T–H₂O pseudosections. The application of the Na/K and Si/Al ratios in melt yielded P–T conditions close to 13 kbar and 700°C, assigned as the conditions of partial melting. Evaluation of contoured P–T pseudosections for the leucosome composition resulted in conditions of about 10.5 kbar and 700°C for the crystallization of amphibole in the leucosome melt, and 9 kbar and 680°C for complete crystallization of this melt.     

Experimental study of the system H3BO3–NaF–SiO2-H2O at 350–800 °C and 1–2 kbar by the method of synthetic fluid inclusions

The phase state of fluid in the system H₃BO₃–NaF–SiO₂–H₂O was studied at 350–800 °C and 1–2 kbar by the method of synthetic fluid inclusions. The increase in the solubility of quartz and the high reciprocal solubility of H₃BO₃ and NaF in water fluid at high temperatures are due to the formation of complexes containing B, F, Si, and Na. At 800 °C and 2 kbar, both liquid and gas immiscible phases (viscous silicate-water-salt liquid and three water fluids with different contents of B and F) are dispersed within each other. The Raman spectra of aqueous solutions and viscous liquid show not only a peak of [B(OH)₃]⁰ but also peaks of complexes [B(OH)₄]^–, polyborates [B₄O₅(OH)₄]^2–, [B₃O₃(OH)₄]^–, and [B₅O₆(OH)₄]^–, and/or fluoroborates [B₃F₆O₃]^3–, [BF₂(OH)₂]^–, [BF₃(OH)]^–, and [BF₄]^–. The high viscosity of nonfreezing fluid is due to the polymerization of complexes of polyborates and fluorine-substituted polyborates containing Si and Na. Solutions in fluid inclusions belong to P–Q type complicated by a metastable or stable immiscibility region. Metastable fluid equilibria transform into stable ones owing to the formation of new complexes at 800 ºC and 2 kbar as a result of the interaction of quartz with B-F-containing fluid. At high concentrations of F and B in natural fluids, complexes containing B, F, Si, and alkaline metals and silicate-water-salt dispersed phases might be produced and concentrate many elements, including ore-forming ones. Their transformation into vitreous masses or viscous liquids (gels, jellies) during cooling and the subsequent crystallization of these products at low temperatures (300–400 °C) should lead to the release of fluid enriched in the above elements.     

27Al, 29Si,and 23Na MAS NMR study of an Al,Si ordered alkali feldspar solid solution series

Solid-state ²⁷Al, ²⁹Si and ²³Na MAS NMR spectra have been obtained for an Al,Si ordered low albite to low microcline ion exchange series for which unit-cell parameters and ²⁹Si NMR data have previously been reported. ²⁷Al δ_i vary continuously with composition from 63.4 (±0.5) ppm for albite to 58.9 (±0.5) ppm for microcline, and parallel the ²⁹Si chemical shifts assigned to the T2m-site. The ²⁷Al and ²⁹Si chemical shifts for this series correlate well with composition-dependent lattice parameters, most notably cell volume and the angle [201]¹b. The linewidths of the ²⁹Si and ²⁷Al resonances indicate a significant amount of structural disorder in the intermediate compositions due to Na, K substitution. The 1 σ width of the distribution of average Si-O-T angles for each T-site is estimated to be about 1° for the Or33 sample. The average ²³Na δ_i varies monotonically from -8.5 (±1) ppm for albite to -24.3 (±1)ppm for Or83. Similarly, the average ²³Na nuclear quadrupole coupling constant decreases from 2.60 to 1.15 (±0.05) MHz and the asymmetry parameter of the electric field gradient increases from 0.25 to 0.6 with increasing K-content from albite to Or83. The observed variations in the quadrupole coupling parameters are consistent with simple electrostatic calculations. Higher resolution ²³Na spectra of the intermediate compositions obtained at 11.7 T indicate the presence of an inhomogeneous linebroadening which is related to the distribution of Na-environments. A model based on a random distribution of local compositions does not simulate the spectra, suggesting that the distribution of Na is skewed toward Na-rich clusters. Observation of the ²³Na NMR lineshape of Or49 after short periods of heat treatment indicate that ²³Na NMR is very sensitive to the changes in the Na, K distribution accompanying the early stages of exsolution. Reversible changes occur after heating at 530° C for 3 h, whereas heating at 600° C produces no changes, possibly bracketing the position of the coherent spinodal for Al, Si ordered alkali feldspars at this composition.     

The effect of composition on the ferric-ferrous ratio in basaltic liquids at atmospheric pressure

The effects on the ferric-ferrous ratio of varying individual components in a dry basaltic liquid have been determined at atmospheric pressure and constant oxygen fugacity (fO₂). Experiments were conducted by suspending 100 mg samples from pt loops at 1200°C (fO₂ = 10^?8atm) and 1360°C (fO₂ = 10^?6atm) in an atmosphere controlled by mixtures of CO₂ and H₂. A microanalytical wetchemical technique and the electron microprobe were used to determine the composition of the resulting basaltic glasses. In order of decreasing significance, the addition of oxides of K, Na, Si, Al, or Ca produces an increase in the ferric-ferrous ratio of the melt at 1200°C. The change in the ferric-ferrous ratio produced by component addition is less at 1360°C than at 1200°C.     

Stability of phlogopite-quartz and sanidine-quartz: A model for melting in the lower crust

The melting of phlogopite-quartz and sanidine-quartz under vapor-absent conditions and in the presence of H₂O-CO₂ vapor have been determined from 5–20 kbar. In the lower crust (P=6–10 kbar), phlogopite + quartz melts incongruently to enstatite + liquid at temperatures as low as 710° C in the presence of H₂O. When the activity of water is sufficiently reduced by addition of CO₂, phlogopite + quartz undergoes a dehydration reaction to enstatite + sanidine + vapor, for example at 790±10° C, 5 kbar, with \(X_{H_2 O}^V\) =0.35. In the absence of vapor, phlogopite + quartz is stable up to a maximum temperature of 900° C in the crust; at higher temperatures this assemblage melts incongruently to enstatite + sanidine + liquid. The melting of sanidine-quartz in the presence of H₂O-CO₂ vapor shows marked topological differences from melting in the system albite-H₂O-CO₂, and as a result, apparent activity coefficients for water calculated from sanidine-quartz H₂O-CO₂ are less than those calculated from albite-H₂O-CO₂ by up to a factor of five. These data shed light on anatexis in the lower crust, but uncertainties related to ordering of Al and Si in natural and synthetic micas forestall a more rigorous analysis. Nevertheless, maximum temperatures for some granulite terranes can be established.     

Experimental determination of corundum solubilities in pure water between 400–700°C and 1–3 kbar

Experimentally reversed corundum solubilities in pure water at 400° to 700°C and 0.7 to 3 kbar yield values of dissolved aluminum that range from 1–4 ppm Al. At constant pressure the solubility shows a sigmoidal behavior with a slight maximum at 500°C and minimum at 600°C. Corundum solubility increases with increasing pressure at constant temperature. The dissolved aluminum appears to form an uncharged, but polar species under these conditions probably of the form Al(OH)₃⁰.     

Aluminous reaction textures in orthoamphibole-bearing rocks: the pressure–temperature evolution of the high-grade Proterozoic of the Bamble sector, south Norway

Aluminous reaction textures in orthoamphibole-bearing rocks from the Froland area, Bamble, south Norway, record the prograde pressure–temperature path of the high-grade Kongsbergian Orogeny (c. 1600–1500 Ma) and the low–mid amphibolite facies overprint during the Sveconorwegian Orogeny (c. 1100–1000 Ma). The rocks contain anthophyllite/gedrite, garnet, cordierite, biotite, quartz, andalusite, kyanite, Cr-rich staurolite, tourmaline, ilmenite, rutile and corundum in a variety of parageneses. The P–T path is deduced from petrographic observations, mineral chemistry and zoning, geothermometry and (N)FMASH equilibria. The results indicate the sequence of metamorphic stages outlined below. (a) An M₁ phase characterized by the presence of strongly deformed andalusite, gedrite and tourmaline. (b) An M₂ phase with the development of kyanite after andalusite and the growth of staurolite associated with strong Na–Al–Mg zoning in orthoamphibole, indicating an increase in pressure (4 8 kbar) and temperature (500° 650°C). (c) Pressure decrease at high P (6–7 kbar) and high T (600–700 °C) during M_3a with the production of cordierite ° Corundum between kyanite, staurolite and orthoamphibole and cordierite growth between corundum and orthoamphibole. (d) Temperature increase to 740 ± 60 °C and 7 kbar; static growth of garnet (M_3b) at the metamorphic climax (peak T). The heat supply necessary to explain the temperature increase between the M_3a and M_3b phases is correlated with synkinematic enderbitic–charnockitic and basic intrusions in the Arendal granulite facies terrain. (e) M_3b metamorphic conditions were followed by an initial isobaric cooling path (early M₄) and late-stage pressure decrease (late M₄). Early M₄ conditions of 6–7 kbar and 550–600 °C, assuming P_H2O < P_total are indicated by a retrograde talc–kyanite–quartz assemblage in late quartz–cordierite veins. Late M₄ conditions of 3–4 kbar and 420–530 °C are inferred from a kyanite–andalusite–chlorite–quartz assemblage in vein-cordierite. The M₁–M₃ stages are interpreted as being the result of the same metamorphic P–T path, which was caused by both tectonic and magmatic thickening. A prolonged crustal residence time is proposed for the Bamble sector before uplift during the later stages of M₄ occurred.     

The effect of feldspar on quartz-H2O−CO2 dihedral angles at 4 kbar,with consequences for the behaviour of aqueous fluids in migmatites

An investigation was made of the effect of trace amounts of feldspar (Na and/or K) on dihedral angles in the quartz-H₂O-CO₂ system at 4 kbar and 450–1050°C. Quartz-quartz-H₂O dihedral angles in feldspar-bearing quartz aggregates are observed to be the same as those in pure quartz aggregates at temperatures below 500°C. Above this temperature, they decrease with increasing temperature until the solidus. The final angle at the inception of melting is about 65° for microcline-quartz-H₂O and microcline-albite-quartz-H₂O, and much less than 60° (the critical value for formation of grain-edge fluid channels in an isotropic system) for the albite-quartz-H₂O system. CO₂ was observed to produce a constant quartz-quartz-fluid dihedral angle of 97° in feldspar-bearing quartz aggregates at all temperatures studied. Also examined were the dihedral angles for the two co-existing supersolidus fluids in quartz aggregates. In all systems the quartz-volatile fluid angle is greater than 60°, whereas the quartz-melt angle is lower than 60°. Both super-solidus angles decrease with increasing temperature. The transition from nonconnected to connected poro- sity with increasing temperature observed in the quartz-albite-H₂O system some tens of degrees below the solidus (termed a permeability transition), if a common feature of rocks near their melting points, will play an important role in controlling the permeability of high-grade rocks to aqueous fluids. Received: 27 October 1993 / Accepted: 11 July 1994     

A method of calculating quartz solubilities in aqueous sodium chloride solutions

The aqueous silica species that form when quartz dissolves in water or saline solutions are hydrated. Therefore, the amount of quartz that will dissolve at a given temperature is influenced by the prevailing activity of water. Using a standard state in which there are 1,000 g of water (55.51 moles) per 1,000 cm³ of solution allows activity of water in a NaCl solution at high temperature to be closely approximated by the effective density of water, p_e, in that solution, i.e. the product of the density of the NaCl solution times the weight fraction of water in the solution, corrected for the amount of water strongly bound to aqueous silica and Na⁺ as water of hydration. Generally, the hydration of water correction is negligible.The solubility of quartz in pure water is well known over a large temperature-pressure range. An empirical formula expresses that solubility in terms of temperature and density of water and thus takes care of activity coefficient and pressure-effect terms. Solubilities of quartz in NaCl solutions can be calculated by using that equation and substituting p_e, for the density of pure water. Calculated and experimentally determined quartz solubilities in NaCl solutions show excellent agreement when the experiments were carried out in non-reactive platinum, gold, or gold plus titanium containers. Reactive metal containers generally yield dissolved silica concentrations higher than calculated, probably because of the formation of metal chlorides plus NaOH and H₂. In the absence of NaOH there appears to be no detectable silica complexing in NaCl solutions, and the variation in quartz solubility with NaCl concentration at constant temperature can be accounted for entirely by variations in the activity of water.The average hydration number per molecule of dissolved SiO₂ in liquid water and NaCl solutions decreases from about 2.4 at 200°C to about 2.1 at 350°C. This suggests that H₄SiO₄ may be the dominant aqueous silica species at 350°C, but other polymeric forms become important at lower temperatures.     

Metamorphic evolution of a subduction complex, South Shetland Islands, Antarctica

A subduction complex composed of ocean floor material mixed with arc-derived metasediments crops out in the Elephant Island group and at Smith Island, South Shetland Islands, Antarctica, with metamorphic ages of 120–80 Ma and 58–47 Ma, respectively. Seven metamorphic zones (I–VII) mapped on Elephant Island delineate a gradual increase in metamorphic grade from the pumpellyite–actinolite facies, through the crossite–epidote blueschist facies, to the lower amphibolite facies. Geothermometry in garnet–amphibole and garnet–biotite pairs yields temperatures of about 350 °C in zone III to about 525 °C in zone VII. Pressures were estimated on the basis of Si content in white mica, Al₂O₃ content in alkali amphibole, Na^M4/Al^IV in sodic-calcic and calcic amphibole, Al^VI/Si in calcic amphibole, and jadeite content in clinopyroxene. Mean values vary from about 6–7.5 kbar in zone II to about 5 kbar in zone VII. Results from the other islands of the Elephant Island group are comparable to those from the main island; Smith Island yielded slightly higher pressures, up to 8 kbar, with temperatures estimated between 300 and 350 °C. Zoned minerals and other textural indications locally enable inference of P–T –t trajectories, all with a clockwise evolution. A reconstruction in space and time of these P–T –t paths allows an estimate of the thermal structure in the upper crust during the two ductile deformation phases (D₁ & D₂) that affected the area. This thermal structure is in good agreement with the one expected for a subduction zone. The arrival and collision of thickened oceanic crust may have caused the accretion and preservation of the subduction complex. In this model, D₁ represents the subduction movements expressed by the first vector of the clockwise P–T–t path, D₂ reflects the collision corresponding to the second vector with increasing temperature and decreasing pressure, and D₃ corresponds to isostatic uplift accompanied by erosion, under circumstances of decreasing temperature and pressure.     

Stability of fluorite and titanite in a calc-silicate rock from the Vizianagaram area, Eastern Ghats Belt, India

In the Vizianagaram area (E 83°29.442′; N 18°5.418′) of the Eastern Ghats Belt, India, a suite of graphite‐bearing calc‐silicate granulites, veined by syenitic rocks, developed wollastonite‐rich veins at 6–7 kbar and > 850 °C. During subsequent near‐isobaric cooling wollastonite was replaced by calcite + quartz and a graphic intergrowth of fluorite + quartz ± clinopyroxene. Titanite with variable Al and F contents is present throughout the rock. Combining the compositional variation of titanite and recent experimental data, it is demonstrated that the mineral assemblage, the composition of coexisting fluids and the mobility of Al exert a far greater control on the composition of titanite than pressure, temperature or the whole rock composition. Thermodynamically computed isothermal–isobaric logf_O2– logf_CO2 and logf_F2– logf_O2 grids in the systems Ca–Fe–Si–O–F (CISOF; calcite‐free) and Ca–Fe–Si–O–F–C–H (CISOFV; calcite‐present) demonstrate the influence of bulk rock and fluid compositions on the stability of the fluorite‐bearing assemblages in diverse geological environments and resolve the problem of the stability of titanite in fayalite + fluorite‐bearing rocks in the Adirondacks. The mineralogy of the studied rocks and the topological constraints tightly fix the logf_O2, logf_F2 and logf_CO2 at ?15.8, ?30.6 and 4.1, respectively, at 6.5 kbar and c. 730 °C. Because of the similarity in the P–T conditions, the compositions of pore fluids in the fluorite‐bearing assemblages of the Adirondacks and the Eastern Ghats Belt have been compared.     

Évolution pression–température des amphibolites de la zone axiale au cours du métamorphisme hercynien des Pyrénées orientales

Thin levels of amphibolites from the Canigou, Albères and Cap de Creus massifs have been studied in order to investigate their pressure and temperature evolution during time. P and T values have been calculated using the amphibole–plagioclase–quartz thermo-barometer. Si, Al, Mg and Fe of zoned amphiboles have been analysed from core to rim by microprobe. By combining the results obtained from several (or different) crystals, P–T–t paths have been determined using the amphibole-plagioclase-quartz equilibriums. In the Canigou Massif, the amphibolites have recorded anti-clockwise P–T–t paths around a peak of metamorphism located at about 650?°C–6.1 kbar, whereas in the Albères Massif, the calculated P–T–t paths of amphibolites near the paragneisses are retrograde only, from 600?°C–5 kbar to 450?°C–2.5 kbar, but one cummingtonite-bearing amphibolite has also recorded an anti-clockwise evolution around 650?°C–4.5 kbar. The retrograde P–T–t paths recorded for amphibolites from the ‘Cap de Creus’ Massif are retrograde only, from 650?°C–6 kbar and 400?°C–1 kbar. To cite this article: C. Triboulet et al., C. R. Geoscience 337 (2005).     

The compositional variation of synthetic sodic amphiboles at high and ultra-high pressures

Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H₂O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H₂O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H₂O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of Al^IV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [Na^AAl^IV]<=>[□^ASi] (edenite) toward nyböite, and [Na^(M4)Al^VI]<=>[Mg^(M4)Mg^VI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.     

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.