Modelling the structure of the metastable phases in the reaction sequence kaolinite-mullite by X-ray scattering experiments

The crystal structure of two kaolinites with a different degree of planar disorder and their high temperature (HT) decomposition products have been investigated by means of symmetrical transmission powder X-ray diffractometry and the subsequent calculation of the radial distribution function (RDF). An ordered and a disordered kaolinite (international standard Kga-1 and Kga-2) were selected along with their HT reaction products at 600°C (metakaolinite) and at 900°C (mullite precursor). The calcinations and quenches have been carried out “ex-situ” prior to the data collection. The procedure for collection and reduction of the data and their interpretation is outlined. The structural characterization of the HT phase transformations is obtained by qualitative analysis of the RDF curves and is related to the extent of planar disorder in the original material. A model for the structure of metakaolinite is proposed on the basis of the present experiments, and of a review of literature data. According to this model, the structure of metakaolinite displays an almost uncollapsed structure with a short-range order in which Al is mainly in four-fold coordination. An “ab initio” modelling of the RDF curves provides a quantitative evaluation of the proposed structural model. Differences in the HT products from different kaolinites are directly correlated with the density of stacking faults in the starting kaolinites. Moreover the structure of the precursor of mullite is described and discussed with respect to the literature data. The nature and role of γ-alumina is discussed as well. Finally the DTA exothermic peak of kaolinite is interpreted in the light of the proposed general model. Received: 18 March 1997 / Revised, accepted: 26 October 1997     

Kinetic study of the kaolinite-mullite reaction sequence. Part I: Kaolinite dehydroxylation

The decomposition reaction of kaolinite has been investigated as a function of the defectivity of the starting material and the temperature of reaction. Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation, both under a constant heating rate (heating rates from 10 to 100° C/min) and in isothermal conditions (in the temperature range 500 to 700° C). The apparent activation energy of the dehydroxylation process is different for kaolinites exhibiting a different degree of stacking fault density. The results of the analysis of the kinetic data indicate that the starting reaction mechanism is controlled by diffusion in the kaolinite particle. The diffusion process is dependent on the defective nature of both kaolinite and metakaolinite. At high temperatures, and at higher heating rates, the reaction mechanism changes and the resistance in the boundary layer outside the crystallites becomes the rate-limiting factor, and nucleation begins within the reacting particle. During the final stage of the dehydroxylation process the reaction is limited by heat or mass transfer, and this might be interpreted by the limited diffusion between the unreacted kaolinite domains and the metakaolinite matrix.     

Dissolution of well and poorly ordered kaolinites by an aerobic bacterium

Previous research by our group (e.g., [Chem. Geol. 132 (1996) 25; Geochim. Cosmochim. Acta 64 (2000) 1363]) has shown that an aerobic Pseudomonas mendocina bacterium enhances Fe(hydr)oxide dissolution in order to obtain Fe under Fe-limited conditions. The P. mendocina is incapable of utilizing Fe as a terminal electron acceptor and requires several orders of magnitude lower Fe concentrations than do dissimilatory Fe reducing bacteria. The research reported here compared the effects of the P. mendocina on dissolution of well and poorly ordered Clay Minerals Society Source Clay kaolinites KGa-1b and KGa-2, respectively, under Fe-limited conditions. KGa-1b and KGa-2 contain 0.04 and 0.94 bulk wt.% Fe, respectively, and their surface Fe/Si atomic RATIOS=0.008 and 0.012. Following strong cleaning of the kaolinites in 5.8 M HCl at 85 °C, the surface Fe/Si atomic ratios decreased to 0.004 and 0.008, respectively. Both kaolinites also developed a Si-enriched surface precipitate upon strong cleaning.

Because the P. mendocina take up Fe, we could not measure Fe release from the kaolinite directly, but rather had to monitor it indirectly by comparing microbial populations sizes under Fe-limited growth conditions. We found that microbial growth on uncleaned, weakly cleaned, and strongly cleaned kaolinites increased with the amount of Fe readily available to organic ligands as estimated by dissolution in 0.001 M oxalate (pH 3). This suggests that it is the amount of readily accessible Fe that controls Fe acquisition and hence microbial growth. The trend is based on only a relatively small range of kaolinite Fe contents, and the research thus needs to be expanded to include kaolinites with a broader range of bulk and surface Fe concentrations.

Significant enhancement of Al release was observed in the presence of the bacteria, along with generally some enhancement of Si release. This enhancement of kaolinite dissolution could be related to an observed pH increase from 7–8 to 9 in the presence of the bacteria and/or to production of Al chelating agents. The P. mendocina produce a variety of organic exudates, including siderophores [Chem. Geol. 132 (1996) 25; Geomicrobiology (2001b)], and further studies into the effects of the siderophores on Al complexation and on kaolinite dissolution are ongoing.     

Grain boundary diffusion of oxygen,potassium and calcium in natural and hot-pressed feldspar aggregates

 Grain boundary diffusion rates of oxygen, potassium and calcium in fine-grained feldspar aggregates were determined experimentally. The starting materials were a natural albite rock from the Tanco pegmatite and aggregates hot-pressed from fragments of Amelia albite or Ab, Or and An composition glasses. The technique employed isotopic tracers (¹⁸O, ⁴¹K, ⁴²Ca) either evaporated onto the surface or in an aqueous solution surrounding the sample, and depth profiling using an ion microprobe (SIMS). From the depth profiles, the product of the grain boundary diffusion coefficient (D′) and effective boundary width (δ) was calculated using numerical solutions to the appropriate diffusion equation. The experimental reproducibility of D′δ is a factor of 3. A separate determination of D′ independent of δ yields an effective grain boundary width of ∼3 nm, consistent with high resolution TEM observations of a physical grain boundary width <5 nm. Oxygen (as molecular water) grain boundary diffusion rates were determined in the Ab and Or aggregates at 450°–800° C and 100 MPa (hydrothermal), potassium rates in Or aggregates at 450°–700° C both at 0.1 MPa (in air) and at 100 MPa (hydrothermal), and calcium rates in An aggregates at 700°–1100° C and 0.1 MPa (in air). Oxygen grain boundary diffusion rates are similar in all three of the Ab aggregates and in the Or aggregate. Potassium and oxygen depth profiles measured in the same samples yield different D′δ values, confirming a diffusional transport mechanism. Potassium diffusion in the Or aggregate has a greater activation energy (216 vs 78 kJ/mol) than oxygen, and the Arrhenius relations cross at ∼625° C. Potassium D′δ values in Or aggregates are about a factor of five greater in hydrothermal experiments at 100 MPa than in experiments at 0.1 MPa in air. Calcium grain boundary diffusion rates in An aggregates are 4 to 5 orders of magnitude slower than potassium in Or and have a greater (291 kJ/mol) activation energy. This suggests that differences in formal charge and/or size of diffusing species may play an important role in their relative grain boundary diffusion rates. Received: 24 December 1993 / Accepted: 16 June 1994     

Electrical properties of opal-CT

 The electrical properties of opal-CT are validated at temperatures from 600 to 840 °C and frequencies from 5 Hz to 10 MHz. The opals are hydrothermal, containing less than 11270 ppm total of Al, Fe, Ca, Na, and K, and from 1.17 to 17.63 wt% H₂O interstitial and structural. Opal-CT shows fine crystallites, measuring from 19.4 to 22.7 μm, of an ordered tridymite-M stratification with high-cristobalite, embedded in a non-crystalline matrix. When heated to 600 °C, the non-crystalline phase devitrifies to the same stacked high-cristobalite-tridymite-M crystals. Opals containing less than 2070 ppm of cationic impurities are characterized by one single high-frequency complex impedance arc corresponding to the bulk polarization of the crystalline phase, of capacitances between 25 and 30×10⁻¹² F and resistances from 132 to 890 ohm. Opals having over 6300 ppm of cationic impurities show two superimposed high- and low-frequency complex impedance arcs. The high-frequency arc corresponds to the bulk polarization of the crystalline phase, of capacitance between 8 and 15.7×10⁻¹² F and resistance from 14 to 236 ohm, less than the capacitance of 0.25 to 0.53×10⁻⁹ F and resistance from 26 to 360 ohm of the non-crystalline minor intergranular material represented by the low-frequency impedance arc. The electric module shows one single vertex, ascribed to the bulk polarization of the crystalline phase. The conductivities are from 10⁻⁷ to 10⁻⁴ ohm⁻¹cm⁻¹, in the range of poor ionic conductors, essentially constant below 1.8 kHz, rapidly increasing at higher frequencies, due to ionic and electronic charge carriers. The activation energy changes between 0.905 and 1.003 eV for the conduction mechanism in the crystalline phase and from 0.924 to 1.087 eV in the non-crystaline phase. X-ray diffraction and impedance spectroscopy confirm that opal-CT is a crystalline stacked sequence of tridymite-M and cristobalite-high, in a non-crystalline matrix. Received October 20, 1995/Revised, accepted June 15, 1996     

Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Bertaux

 Ni-saturated montmorillonite from Camp-Bertaux heated at different temperatures has been studied by X-ray powder diffraction, X-ray absorption (EXAFS) and vibration IR spectroscopy. Analysis of the experimental data has shown that heating of samples at temperatures higher than 150° C was accompanied by migration of Ni cations into vacant cis-octahedra of 2:1 layers. In the octahedral sheet the Ni cation has two “heavy” (Fe) and four “light” (Al and Mg) nearest octahedral cations. A model for the octahedral cation distribution in Camp-Bertaux montmorillonite was proposed in which Fe and Mg octahedral cations are segregated in small clusters. Received July 7, 1996 / Revised, accepted August 23, 1996     

Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO₂ partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L⁻¹ to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.     

Petrology of ultramafic xenoliths from Kishyuku Lava,Fukue-jima,Southwest Japan

 Ultramafic xenoliths are found in Kishyuku Lava, Fukue-jima, Southwest Japan. These include spinel lherzolite, harzburgite and dunite, as well as pyroxenite. The compositions of the constituent minerals of the peridotite xenoliths are in the range of upper mantle peridotites. Variable Cr/(Cr+Al) ratios (0.1–0.5) of spinel, together with a limited range in olivine composition (Fo₉₀–Fo₉₂), indicate that the xenoliths are derived from slightly to highly depleted residual mantle. The combination of previously published clinopyroxene-olivine geothermobarometry and clinopyroxene-orthopyroxene geothermometry applied to the xenoliths yields a high geotherm of 1070° C at 1.0 GPa up to 1200° C at 2.2 GPa. Existence of such depleted upper mantle is compatible with the existing model of asthenospheric injection during the rifting of the Northeast China and the Japan Sea. The high geotherm is caused by thermal perturbation due to the injection of the hot asthenosphere and/or post-rifting uprise of mantle diapirs since 11 Ma. Received: 15 May 1995 / Accepted: 3 January 1996     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

Calcium self-diffusion in diopside at high temperature: implications for transport properties

We have investigated ⁴⁴Ca self-diffusion in natural diopside single crystals (containing ∼2 atomic % Fe) at temperatures up to 1320 °C (i.e. 30 °C below the nominal melting point). Oxygen fugacity was controlled by gaseous mixtures. Diffusion profiles ranging from ∼50 to 500 nm were analysed by Rutherford Back-Scattering Spectrometry (RBS). The present results are complementary to previous studies, and show that in both synthetic (Fe-poor) and natural (Fe-rich) diopside, there are two different diffusion regimes for Ca with a transition at ∼1230±15 °C. Below this temperature diffusion is characterised by an activation enthalpy of ∼284±10 kJ/mol, while at higher temperatures it increases up to ∼1006±75 kJ/mol. These regimes are proposed to be respectively extrinsic and intrinsic. For the intrinsic regime Ca self-diffusion may involve Ca-Frenkel point defects. These are pairs of a vacancy on a M₂ site and a calcium cation on an interstitial (normally unoccupied) site. The concentration of such point defects depends only on temperature, and it is especially important at very high temperatures. The activation enthalpy for intrinsic diffusion may represent the half defect formation enthalpy plus the migration enthalpy for movement through interstitial sites. For the extrinsic regime we propose Ca self-diffusion to involve extrinsic interstitial point defects with concentration proportional to ()^{–0.19±0.03}. We suggest that for both regimes, Ca diffusion involves the well known M₃ sites in the octahedral layers, as well as sites in the tetrahedral layers, that we call M_4. These sites are especially convenient to explain the observed isotropic diffusion. Increasing concentration of Ca-Frenkel point defects may be related to the onset of premelting, which affects the thermodynamic properties of Fe-“free” diopside above 1250 °C. In the light of the present results, premelting is also expected to occur in natural Fe-bearing diopside and it could strongly influence its thermodynamic and transport properties. Subsequently, in deep upper mantle conditions (T≈1250 °C–1300 °C) where premelting could occur, diffusional cation exchanges with surrounding phases and diffusion controlled creep might be facilitated. Finally, our diffusion data support a previous suggestion that electrical conductivity may be electronic rather than ionic. Received: 17 December 1997 / Revised, accepted: 17 April 1998     

“偏高岭石—碱—水”体系中4A沸石晶体生长规律及其机理探讨

煅烧高岭土与氢氧化钠的水热反应体系中，偏高岭石不仅为４Ａ沸石的形成提供了物质基础，而且为晶核的形成提供了有利界面。４Ａ沸石的晶核总是优先形成于发生了溶解的偏高岭石表面，而晶体生长的方式则受偏高岭石颗粒大小的影响。随着晶体的大量生长，偏高岭石逐渐消失，与此同时，产生了二次成核作用，晶体在先成的４Ａ沸石晶体表面生长，形成双晶。在整个反应过程中，液相中的［Ａｌ２Ｏ３］及［ＳｉＯ２］浓度的变化与４Ａ沸石晶体生成具有一定对应关系。这表明，偏高岭石不断溶解，固相的Ａｌ２Ｏ３·２ＳｉＯ２不断转化为液相的Ａｌ２Ｏ３和ＳｉＯ２。沸石晶体的生成是以液相各组分浓度的过饱和为动力的，为液相生成机理     

Volume and grain boundary diffusion of calcium in natural and hot-pressed calcite aggregates

 Calcium self-diffusion rates in natural calcite single crystals were experimentally determined at 700 to 900° C and 0.1 MPa in a stream of CO₂. Diffusion coefficients (D) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The Arrhenius parameters yield an activation energy (Q)=382±37 kJ/mol and pre-exponential factor (D₀)=0.13 m²/s, and there is no measurable anisotropy. Calcium grain boundary diffusion rates were experimentally determined in natural (Solnhofen) limestone and hot-pressed calcite aggregates at 650° to 850° C and 0.1 to 100 MPa pressure. The Solnhofen limestone was first pre-annealed for 24 h at 700° C and 100 MPa confining pressure under anhydrous conditions to produce an equilibrium microstructure for the diffusion experiments. Values for the product of the grain boundary diffusion coefficient (D′) and the effective grain boundary diffusion width (δ) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The results show that there is no measurable difference between D′δ values obtained for pre-annealed Solnhofen samples at 0.1 and 100 MPa or between hot-pressed calcite aggregates and pre-annealed Solnhofen samples. The temperature dependence for calcium grain boundary diffusion in Solnhofen samples annealed at 0.1 MPa is described by the Arrhenius parameters D^′ ₀δ=1.5×10⁻⁹ m³/s and Q=267±47 kJ/mol. Comparison of the results of this study with previously published data show that calcium is the slowest volume diffusing species in calcite. The calcium diffusivities measured in this study place constraints on several geological processes that involve diffusive mass transfer including diffusion-accommodated mechanisms in the deformation of calcite rocks. Received: 19 December 1994/Accepted: 30 June 1995     

Petrology of a 2.41 Ga remarkably fresh komatiitic basalt lava lake in Lion Hills,central Vetreny Belt,Baltic Shield

 In the central Vetreny Belt, southeastern Baltic Shield, an areally extensive 110 m deep lava lake is exposed consisting of remarkably fresh differentiated komatiitic basalt. During eruption, the liquid had a temperature of 1380–1400 °C and contained ∼15% MgO. The lava ponded in a large topographic depression soon after eruption. The differentiation of the lava lake was controlled by settling of transported olivine and chromite phenocrysts and caused the origin of prominent internal layering. The last portions of the trapped liquid crystallized at temperatures of 1250– 1070 °C. A Sm-Nd isochron of 2410±34 Ma for whole rock samples, olivine, augite and pigeonite separates from the lava lake provides a reliable estimate for the time of formation of the uppermost sequences in the Vetreny Belt. This age is in good agreement with the Sm-Nd and Pb-Pb isochron ages of 2449±35 and 2424±178 Ma for the volcanic rocks from the same stratigraphic level in the northwestern Vetreny Belt. Modeling of Nd-isotopes and major and trace elements shows that the komatiitic basalts at Lion Hills may have had a komatiite parent depleted in highly incompatible elements. It can be shown that this initial liquid was contaminated by 7–9% of Archaean upper crustal material from the adjacent Vodla and Belomorian Blocks en route to the surface thus acquiring the observed geochemical and isotope signatures including relative enrichment in Zr, Ba, and LREE, negative Nb- and Ti-anomalies and ɛNd(T) of −1. Received: 8 December 1995/Accepted: 26 March 1996     

Hydrothermal Alteration Zoning and Kinetic Process of Mineral-Water Interactions

This study reports the kinetic experimental results of albite in water and in KCI solution at 22 MPa in the temperature range of 25 to 400℃. Kinetic experiments have been carried out in an open flow-through reaction system (packed bed reactor). Albite dissolution is always incongruent in water at most temperatures, but becomes congruent at 300℃ (close to the critical point 374℃). At temperatures from 25 to 300℃, the incongruent dissolution of albite is reflected by the fact that sodium and aluminum are easily dissolved into water; from 300 to 400℃ it is reflected by silicon being more easily dissolved in water than Al and Na. Maximum albite dissolution rates in the flow hydrothermal systems have been repeatedly observed at 300℃, independent of flow rates.The kinetic experiments of albite dissolution in a KCl aqueous solution (0.1 mol KCl) indicate that the dissolution rate of albite increases with increasing temperature. Maximum silicon release rates of albite have been observed at 400℃, while ma     

Ca–Mn exchange between grossular and MnCl2 solutions at 2 kbar and 600°°C: reaction mechanism and evidence for non-ideal mixing in spessartine-grossular garnets

 The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca₃Al₂Si₃O₁₂+3Mn²⁺(aq) ⇔ Mn₃Al₂Si₃O₁₂+3Ca²⁺(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich (X ^gt _Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln K_D versus X ^gt _Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w ^gt _CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w ^gt _CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al₂SiO₅-quartz barometer will not be increased by more than 0.2 kbar. Received: 18 January 1995/Accepted: 4 June 1996     

Metamorphic reactions between fluid inclusions and mineral hosts. I. Progress of the reaction calcite+quartz=wollastonite+CO2 in natural wollastonite-hosted fluid inclusions

 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO₂. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)_Cleq=64–73 wt%; X _{CO 2}≤0.02]; (2) low density vapour-rich CO₂-bearing inclusions [Th(L-V)≈500±100° C; X _{CO 2}=0.22–0.44; X _NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm⁻³. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H₂O-CO₂-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO₂=Cc+Qz of the host with the CO₂-proportion of the fluid during retrogression. All of the CO₂ was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H₂O-CO₂-NaCl, along with f _{CO 2}-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995     

Moderate pressure metamorphism and anatexis due to anorthosite intrusion,western Adirondack Highlands,New York

 Garnet-sillimanite-biotite gneiss near Port Leyden, in the western Adirondack Highlands, New York, contains mineral assemblages and textures that formed during high temperature metamorphism and anatexis at mid-crustal pressures. Evidence for melting includes thin, plagioclase-rich veins, sieve textures in biotite, and the presence of small, euhedral garnet neoblasts. Hercynite-silicate equilibria in combination with the solidus for biotite dehydration melting indicate metamorphic pressure was between 4 and 6.4 kbar at the temperature of melting (ca. 735° C). The gneiss is intruded by a small, discordant Fe-Ti oxide-apatite (nelsonite) dike. Reported field occurrences of nelsonite demonstrate its common association with anorthosite plutons. Although no anorthosite bodies are exposed in the Port Leyden region, the presence of nelsonite is evidence of anorthositic magmatism in the western Adirondacks. Post-intrusion metamorphism has caused partial apatite recrystallization and produced a weak foliated texture in the dike. U-Pb ages from zircon and monazite from both the gneiss and the nelsonite dike indicate that these rocks experienced a complex, polymetamorphic history that we interpret to reflect two thermal episodes. An older event is recorded by discordant zircons in the gneiss, which indicate a minimum age of 1129±6 Ma. A linear best fit to the data yields an upper intercept at 1166±53 Ma. This range of ages coincides with anorthosite-suite magmatism in the Adirondacks. A minimum zircon age of 1104±3 Ma was obtained from the nelsonite dike. Lead-loss or late zircon crystallization at about 1020 Ma affected the U-Pb systematics of zircon in the dike. Monazite ages from both rocks also indicate high temperature metamorphism (>700° C) between 1040 and 960 Ma. The older zircon ages and textural relations in the metapelite are viewed as evidence for anatexis at ca. 1150 Ma, and the presence of nelsonite suggests that the intrusion of anorthosite was coincident with partial melting in the gneiss. P-T estimates of metamorphism, therefore, imply that anorthosite was emplaced to about 15 km depth in the western Adirondack Highlands. Received: 13 September 1994 / Accepted: 10 May 1995     

The low-pressure stability of phase A,Mg7Si2O8(OH)6

 Phase A, Mg₇Si₂O₈(OH)₆, is a dense hydrous magnesium silicate whose importance as a host of H₂O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between 3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650^° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750^° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (10⁵ Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H₂O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH ^o _f =−7126±8 kJ mol^-1, S ^o=351 J K^-1 mol^-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite. The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H₂O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO₂–H₂O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase A could crystallise at pressures above approximately 6 GPa. Received: 3 July 1995/Accepted: 14 December 1995     

The partitioning of copper between silicate melts and two-phase aqueous fluids: An experimental investigation at 1 kbar, 800° C and 0.5 kbar, 850° C

 Experiments were performed in the three phase system high-silica rhyolite melt+low-salinity aqueous vapor+hydrosaline brine, to investigate the partitioning equilibria for copper in magmatic-hydrothermal systems at 800° C and 1 kbar, and 850° C and 0.5 kbar. D^aqm/mlt _Cu and apparent equilibrium constants, K^aqm/mlt _Cu,Na, between the aqueous mixture (aqm=quenched vapor+brine) and the silicate melt (mlt) are calculated. D^aqm/mlt _Cu increases with increasing aqueous chloride concentration and is a function of pressure. K^aqm/mlt _Cu,Na=215(±73) at 1 kbar and 800° C and K^aqm/mlt _Cu,Na=11(±6) at 0.5 kbar and 850°C. Decreasing pressure from 1 to 0.5 kbar lowers K^aqm/mlt _Cu,Na by a factor of approximately 20. Data revealed no difference in K^aqm/mlt _Cu,Na or D^aqm/mlt _Cu as a function of the melt aluminium saturation index. Within the 2-phase field the K^aqm/mlt _Cu,Na show no variation with total aqueous chloride, indicating that copper-sodium exchange between the vapor, brine and silicate melt is independent of the mass proportion of vapor and brine. Model copper-sodium apparent equilibrium constants for the hydrosaline brine and the silicate melt revealed a negative dependence on pressure. Model apparent equilibrium constants for copper-sodium exchange between the brine and vapor were close to unity at 1 kbar and 800° C. Received: 27 June 1994/Accepted: 30 March 1995     

The effect of water on the viscosity of a haplogranitic melt under P-T-X conditions relevant to silicic volcanism

 The viscosities of hydrous haplogranitic melts synthesized by hydrothermal fusion at 2 kbar pressure and 800 to 1040° C have been measured at temperatures just above the glass transition and at a pressure of 1 bar using micropenetration techniques. The micropenetration viscometry has been performed in the viscosity range of 10⁹ Pa s to 10¹² Pa s. The samples ranged in water content from 0.4 to 3.5 wt%. For samples with up to 2.5 wt% H₂O, the water contents have been determined using infrared spectroscopy obtained before and after each viscometry experiment to be constant over the duration of the measurements. Above this water content a measurable loss of water occurs during the viscometry. The viscosity data illustrate an extremely nonlinear decrease in viscosity with added water. The viscosity drops drastically with the addition of 0.5 wt% of water and then shallows out at water contents of 2 wt%. An additional viscosity datum point obtained from the analysis of fluid inclusions in a water-saturated HPG8 confirms a near invariance of the viscosity with the addition of water between 2 and 6 wt%. These measurements may be compared directly with the data of Hess et al. (1995, in press) for the effects of excess alkali and alkaline earth oxides on the viscosity of HPG8 (also obtained at 1 bar). The viscosity of the melts, compared on an equivalent molar basis, increases in the order H₂O<(Li₂O<Na₂O< K₂O<Rb₂O,Cs₂O<BaO<SrO<CaO<MgO< BeO). The extraordinary decrease in melt viscosity with added water is poorly reproduced by the calculation scheme of Shaw (1972) for the range of water contents investigated here. The speciation of water in the quenched glasses can be used to quantify the dependence of the viscosity on hydroxyl content. Considering only the hydroxyl groups as active fluidizers in the hydrous melts the nonlinearity of the viscosity decrease and the difference with the effects of the alkali oxides becomes larger. Consequences for degassing calcalkaline rhyolite are discussed. Received: 17 August 1995/Accepted: 8 January 1996