Systematic study of liquidas phase relations in olivine melilitite +H2O +CO2 at high pressures and petrogenesis of an olivine melilitite magma

Near-liquidus phase relationships of a spinel lherzolite-bearing olivine melilitite from Tasmania were investigated over a P, T range with varying , , and . At 30 kb under MH-buffered conditions, systematic changes of liquidus phases occur with increasing ( = CO₂/CO₂ +H₂O+olivine melilitite). Olivine is the liquidus phase in the presence of H₂O alone and is joined by clinopyroxene at low . Increasing eliminates olivine and clinopyroxene becomes the only liquidus phase. Further addition of CO₂ brings garnet+orthopyroxene onto the liquidus together with clinopyroxene, which disappears with even higher CO₂. The same systematic changes appear to hold at higher and lower pressures also, only that the phase boundaries are shifted to different . The field with olivine- +clinopyroxene becomes stable to higher with lower pressure and approaches most closely the field with garnet+orthopyroxene+clinopyroxene at about 27 kb, 1160 °C, 0.08 and 0.2 (i.e., 6–7% CO₂+ 7–8% H₂O). Olivine does not coexist with garnet+orthopyroxene+clinopyroxene under these MH-buffered conditions. Lower oxygen fugacities do not increase the stability of olivine to higher and do not change the phase relationships and liquidus temperatures drastically. Thus, it is inferred that olivine melilitite 2927 originates as a 5% melt (inferred from K_{2 O} and P₂O₅ content) from a pyrolite source at about 27kb, 1160 dg with about 6–7% CO₂ and 7–8% H₂O dissolved in the melt. The highly undersaturated character of the melt and the inability to find olivine together with garnet and orthopyroxene on the liquidus (in spite of the close approach of the respective liquidus fields) can be explained by reaction relationships of olivine and clinopyroxene with orthopyroxene, garnet and melt in the presence of CO₂.     

Aluminum partitioning between olivine and ultrabasic silicate liquid to 6 GPa

Trace element analyses of 1-atm and high-pressure experiments show that in komatiite and peridotite, the olivine (OL)/liquid (L) distribution coefficient for Al₂O₃ ( ) increases with pressure and temperature. Olivine in equilibrium with liquid accepts as much as 0.2 wt% Al₂O₃ in solution at 6 GPa. Convergence to equilibrium compositions at this high level is shown by cation diffusion of Al into synthetic forsterite crystals of low-Al contents in the presence of melt. Convergence to low-Al equilibrium compositions at lower P and T is shown by diffusion of Al out of synthetic forsterite with high initial Al content. Isobaric and isothermal experimental data subsets reveal that temperature and pressure variations both have real effects on . Variation in silicate melt composition has no detectable effect on within the limited range of experimentally investigated mixtures. Least-squares regression for 24 experiments, using komatiite and peridotite, performed at 1 atm to 6 GPa and 1300 to 1960°C, gives the best fit equation: Increase in with increasingly higher-pressure melting is consistent with incorporation of a spinel-like component of low molar volume into olivine, although other substitutions possibly involving more complex coupling cannot be ruled out. High P-T ultrabasic melting residues, if pristine, may be recognized by the high calculated from microprobe analyses of Al₂O₃ concentrations in residual olivines and estimated Al₂O₃ concentration in the last liquid removed. In general the low levels of Al in natural olivine from mantle xenoliths suggest that pristine residues are rarely recovered.     

Antigorite-ophicarbonates: Phase relations in a portion of the system CaO-MgO-SiO2-H2O-CO2

The occurrence of critical assemblages among antigorite, diopside, tremolite, forsterite, talc, calcite, dolomite and magnesite in progressively metamorphosed ophicarbonate rocks, together with experimental data, permits the construction of phase diagrams in terms of the variables P, T, and composition of a binary CO₂-H₂O fluid. Equilibrium constants are given for the 30 equilibria that describe all relations among the above phases. Ophicalcite, ophidolomite, and ophimagnesite assemblages occupy partially overlapping fields in the diagram. The upper temperature limit of ophicalcite rocks lies below that of ophidolomite and ophimagnesite. The fluid phase in ophicarbonate rocks has 0.8$$ " align="middle" border="0"> , and there are indications that during their progressive metamorphism is approximately equal to P _total.     

Fe2+-Mg2+ partition between coexisting cordierite and garnet — a discussion of the experimental data

The partition of iron and magnesium between cordierite and garnet depends on as well as temperature. The apparently conflicting experimental data on the values of K _D may be reconciled by considering the pertaining during the different experiments.     

The origin of the high-K latites from Camp Creek,Arizona: constraints from experiments with variable fO2 and a_{{\text{H}}_{\text{2}} {\text{O}}}

Near-liquidus melting experiments were performed on a high-K latite at fO₂'s ranging from iron-wustite-graphite (IWG) to nickel-nickel oxide (NNO) in the presence of a C-O-H fluid phase. Clinopyroxene is a liquidus phase under all conditions. At IWG , the liquidus at 10 kb is about 1,150° C but is depressed to 1,025° C at NNO and . Phlogopite and apatite are near-liquidus phases, with apatite crystallizing first at pressures below 10 kb. Phlogopite is a liquidus phase only at NNO and high . Under all conditions the high-K latites show a large crystallization interval with phlogopite becoming the dominant crystalline phase with decreasing temperature. Increasing fO₂ affects phlogopite crystallization but the liquidus temperature is essentially a function of . The chemical compositions of the near-liquidus phases support formation of the high-K latites under oxidizing conditions (NNO or higher) and high . It is concluded from the temperature of the H₂O-saturated liquidus at 10 kb, the groundmass: crystal ratio and presence of chilled latite margins around some xenoliths that the Camp Creek high-K latite magma passed thru the lower crust at temperatures of 1,000° C or more.     

Water in microcrystalline quartz of volcanic origin: Agates

Agates of volcanic origin, containing the different quartz species, fibrous, length-fast chalcedony (CH), granular fine quartz (FQ), and fibrous, length-slow, to lepidospheric quartzine (QN), have been investigated to evaluate possible relations between microstructure, i.e. crystallite size and texture, refractive indices, densities, contents of trace elements and of water, as well as dehydration behaviour. By means of near infrared spectroscopy, total water contents , could be differentiated quantitatively into contents of molecular water, , and silanole-group water, . Despite the low total water contents of the agates studied ( between 1 and 2 wt.%), near infrared spectroscopy results in reliable data on and .Wall-layering CH consists of fibrous quartz crystals and exhibits higher C-ratios, , than horizontally layered FQ which consists predominantly of granular quartz crystals (C _CH=0.45±0.11 (N=6), C _FQ=0.36±0.10 (N=4). This result is interpreted to be due to analogy with the behaviour of C-ratios in fluid phase-deposited opals-AN (hyalithe) and liquid phase-deposited opals-AG (non-crystalline opal) or -CT (common opal) (Langer and Flörke 1974).Translucent layers of CH show mostly lower refractive indices, when measured parallel than when measured perpendicular to the axes of the quartz fibers. The same is true for milky layers of CH. Crystallite sizes are smaller in the latter than in the former.For all samples studied, exists a positive correlation between at% (1/2Ca+1/2Mg+Na+K+Li) and at% (Al³⁺+Fe³⁺). This indicates that at least parts of (A1³⁺+ Fe³⁺) substitute for Si in the quartz structure. The charge is balanced by incorporation of di- and mono-valent cations in structural interstices. When the quantity at % H⁺, as obtained from , is included into the sum at% (1/2 Me²⁺+Me⁺), the above correlation is destroyed. This result could be indicative for a strong concentration of the Si-OH groups in the surface of the quartz microcrystallites.     

Relationship between fluid-bearing and fluid-absent invariant points and a petrogenetic grid for a greenschist facies assemblage in the system CaO-MgO-Al2O3-SiO2-CO2-H2O

In the 6 component system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂ with 9 solid phases (quartz, plagioclase, epidote, tremolite, talc, chlorite, magnesite, calcite, dolomite) and a fluid phase, all 17 possible fluid-absent reactions have been set up and balanced. Using molar entropy and volume data for the solid phases, these reactions are arranged in P-T space about the 8 possible fluid-absent invariant points after the method of Schreinemakers. Field observations in Ordovician greenschist facies basic volcanics at Sofala N.S.W., indicate that neither talc+epidote nor magnesite+calcite are stable under the conditions of metamorphism. Assuming these conditions to apply to the theoretical study here, the fluid-absent invariant points are arranged in a relative fashion with fluid-absent reactions subdividing P-T space into smaller areas.A scheme which permits a fluid of composition (i.e. a fluid containing CO₂ and H₂O together with other components), is modeled by treating H₂O as a mobile component independent of CO₂, and by allowing values that lie off the locus of binary H₂O-CO₂. Taking into account that neither talc+epidote nor magnesite +calcite is to be permitted, the fluid scheme is used to set up and balance all 39 possible fluid-bearing reactions. These are then arranged about 20 valid fluid-bearing invariant points in space after the method of Korzhinskii and Sehreinemakers.A characteristic solid phase assemblage is defined for each P-T area using chemographic relations inherent from the fluid-absent boundary reactions. The fluid-bearing invariant points that have a solid assemblage compatible with the characteristic assemblage in a particular P-T area are stable within the P-T regime of that area. When these stable fluidbearing invariant points are arranged in a relative fashion in space, they outline a fluid grid which can be used to study the possible effects of local variation in X _fluid over the particular P-T regime.Symbols Used U chemical potential - S entropy - V molar volume - n coefficient of a phase in a reaction - X mole fraction - T temperature - P pressure - F number of degrees of freedom - C number of components - p number of phases - s solid - slope of reaction - 1 quartz - 2 plagioclase - 3 epidote - 4 tremolite - 5 talc - 6 chlorite - 7 dolomite - 8 magnesite - 9 calcite     

Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer

The Al-in-hornblende barometer, which correlates Al^tot content of magmatic hornblende linearly with crystallization pressure of intrusion (Hammarstrom and Zen 1986), has been calibrated experimentally under water-saturated conditions at pressures of 2.5–13 kbar and temperatures of 700–655°C. Equilibration of the assemblage hornlende-biotite-plagioclase-orthoclasequartz-sphene-Fe-Ti-oxide-melt-vapor from a natural tonalite 15–20° above its wet solidus results in hornblende compositions which can be fit by the equation: P(±0.6 kbar) = –3.01 + 4.76 Al _hbl ^tot r ²=0.99, where Al^tot is the total Al content of hornblende in atoms per formula unit (apfu). Al^tot increase with pressure can be ascribed mainly to a tschermak-exchange ( ) accompanied by minor plagioclase-substitution ( ). This experimental calibration agrees well with empirical field calibrations, wherein pressures are estimated by contact-aureole barometry, confirming that contact-aureole pressures and pressures calculated by the Al-in-hornblende barometer are essentially identical. This calibration is also consistent with the previous experimental calibration by Johnson and Rutherford (1989b) which was accomplished at higher temperatures, stabilizing the required buffer assemblage by use of mixed H₂O-CO₂ fluids. The latter calibration yields higher Al^tot content in hornblendes at corresponding pressures, this can be ascribed to increased edenite-exchange ( ) at elevated temperatures. The comparison of both experimental calibrations shows the important influence of the fluid composition, which affects the solidus temperature, on equilibration of hornblende in the buffering phase assemblage.     

An almandine garnet isograd in the Rogers Pass area,British Columbia: The nature of the reaction and an estimation of the physical conditions during its formation

In the Rogers Pass area of British Columbia the almandine garnet isograd results from a reaction of the form: 5.31 ferroan-dolomite+8.75 paragonite+4.80 pyrrhotite+3.57 albite+16.83 quartz+1.97 O₂=1.00 garnet+16.44 andesine+1.53 chlorite+2.40 S₂+1.90 H₂O+10.62 CO₂. The coefficients of this reaction are quite sensitive to the Mn content of ferroan-dolomite.Experimental data applied to mineral compositions present at the isograd, permits calculation of two intersecting P, T equilibrium curves. P=29088–39.583 T is obtained for the sub-system paragonite-margarite (solid-solution), plagioclase, quartz, ferroan-dolomite, and P=28.247 T–14126 is obtained for the sub-system epidote, quartz, garnet, plagioclase. These equations yield P=3898 bars and T=638° K (365° C). These values are consistent with the FeS content of sphalerite in the assemblage pyrite, pyrrhotite, sphalerite and with other estimates for the area.At these values of P and T the composition of the fluid phase in equilibrium with graphite in the system C-O-H-S during the formation of garnet is estimated as: bars, bars, bars, bars, bars, bars, bars, bars, , bars, bars.     

The volatile component of quaternary ignimbrite magmas from the North Island,New Zealand

Ignimbrites from the central North Island consist mainly of glass or its devitrified product (70–95%); their phenocryst mineralogy is varied and includes plag., hyp., ti-mag., ilm., aug., hblende, biot., san., qtz, ol., with accessory apatite, zircon and pyrrhotite. The Fe-Mg minerals can be used to divide the ignimbrites into four groups with hyp.+aug. reflecting high quench temperatures and biot.+hblende +hyp.+aug., low quench temperatures. Oxygen fugacities lie above the QMF buffer curve and even in ignimbrites with low crystal contents the solid phases apparently buffered fO₂. Some ignimbrites contain the assemblage actinolite, gedrite, magnetite and hematite, reflecting post-eruption oxidation. The mineralogy also allows estimation of using pyrrhotite and thence , . The assemblage biotite-sanidine can be used to estimate and thence . Water fugacity is calculated in a variety of ways using both biotite and hornblende as well as the combining reaction . It is high and approaches P _total in most ignimbrites (~4kb) but is lower in unwelded pumice breccias. Comparison of temperature estimates using mineral geothermometers for the various phenocryst phases suggests that the ignimbrite magmas showed temperature differences of 60–100 °C and pressure differences of several kilobars. Individual magma chambers therefore, would have extended over several kilometres vertically. The chemical potential of water may have been constant through the magma.     

An experimental study of the diffusion of oxygen in quartz and albite using an overgrowth technique

Diffusion rates of¹⁸O tracer in quartz ( c, 1 Kb H₂O) and Amelia albite ( 001, 2 Kb H₂O) have been measured, using Secondary Ion Mass Spectrometry (SIMS). A new technique involving hydrothermal deposition of labelled materials has removed the possibility of pressure solution-reprecipitation processes adversely affecting the experiments. Reported diffusion constants are:-quartz ( c), ,Q=98±7 KJ mol^–1 (600–825° C, 1 Kb); Amelia albite ( 001), ,Q=85±7 KJ mol^–1, (400–600° C, 2 Kb). Measured quartz¹⁸O diffusivities decrease discontinuously at the- transition, reflecting strong structural influences. The reported albite data agree with previously recorded studies, but-quartz data indicate significantly lower activation energies. Possible causes of this discrepancy, and some geological consequences, are noted.     

The stability and phase relations of iron chlorite below 8.5 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Iron chlorites with compositions intermediate between the two end-members daphnite (Fe₅Al₂Si₃O₁₀(OH)₈) and pseudothuringite (Fe₄Al₄Si₂O₁₀(OH)₈) were synthesized from mixtures of reagent chemicals. The polymorph with a 7 Å basal spacing initially crystallized from these mixtures at 300 °C and 2 kb after two weeks. Conversion to a 14 Å chlorite required a further 6 weeks at 550 °C. Shorter conversion times were required at higher water pressures. The products contained up to 20% impurities.The maximum equilibrium decomposition temperature for iron chlorite, approximately 550 °C at 2kb, is at an between assemblages (1) and (2) listed below. Synthetic iron chlorite will break down by various reactions with variable P, T, and fugacity of oxygen. For the composition FeAlSi = 523, the sequence of high temperature breakdown products with increasing traversing the magnetite field for P _total = =2kb is: (1) corierite+ fayalite+hercynite; (2) cordierite+fay alite+magnetite; (3) cordierite+magnetite+quartz; (4) magnetite+mullite+quartz. Almandine should replace cordierite in assemblages (1) and (2) but it did not nucleate. The significance of the relationship between iron cordierite and almandine in this system is discussed.At water pressures from 4 to 8.5 kb and at the nickel-bunsite buffer, iron chlorite+quartz break down to iron gedrite+magnetite with temperature 550 to 640 °C along the curve. At temperatures 50 °C greater and along a parallel curve, almandine replaces iron gedrite. For on this buffer curve, almandine is unstable below approximately 4 kb for temperatures to approximately 750 °C.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

Manganese olivine I: Electrical conductivity

To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn₂SiO₄, electrical conductivity () of single crystals was measured along either the [100] or the [010] direction. The experiments were carried out at temperatures T=850–1200 °C and oxygen fugacities atm under both Mn oxide (MO) buffered and MnSiO₃ (MS) buffered conditions. Under the same thermodynamic conditions, charge transport along [100] is 2.5–3.0 times faster than along [010]. At high oxygen fugacities, the electrical conductivity of samples buffered against MS is 1.6 times larger than that of samples buffered against MO; while at low oxygen fugacities, the electrical conductivity is nearly identical for the two buffer cases. The dependencies of electrical conductivity on oxygen fugacity and temperature are essentially the same for conduction along the [100] and [010] directions, as well as for samples coexisting with a solid-state buffer of either MO or MS. Hence, it is proposed that the same conduction mechanisms operate for samples of either orientation in contact with either solid-state buffer.The electrical conductivity data lie on concave upward curves on a log-log plot of vs , giving rise to two regimes with different oxygen fugacity exponents. In the low- regime , the exponent, m, is 0, the MnSiO₃-activity exponent, q, is 0, and the activation energy, Q, is 45 kJ/mol. In the high regime 10^{ - 7} {\text{atm}}} \right)$$ " align="middle" border="0"> , m=1/6, q=1/4–1/3, and Q=45 and 200 kJ/mol for T<1100 °c=" and=">T>1100 °C, respectively.     

Reaction spaces and P-T paths: from amphibole eclogite to greenschist facies in the Austroalpine domain (Oetztal Complex)

The transition from feldspar amphibolite to eclogite is a very wide P-T field that extends from some-where close to 5 kbar where the garnet-amphibole pair starts to appear, to 10–20 kbar at albite-out reaction, then up to 25–30 kbar where an hydrated phase such as amphibole can be stable with pyroxene and garnet. Thus the assemblage garnet (py)+ amphibole (tr)+epidote (cz)±plagioclase (ab)±clinopyroxene (di)±quartz (qz)±fluid is commonly reported in a large number of metamorphic terrains. These mineral phases are complex solid-solutions which adapt to variations in environmental conditions mainly by means of continuous reactions. The reaction space, introduced by. Thompson in 1982a, provides a very elegant and powerful tool to approach these high-variance assemblages. The reactions:

APL computer programs for thermodynamic calculations of equilibria in P-T-X CO 2 space

APL computer programs for the thermodynamic calculation of devolatilization and solid-solid equilibria operate using stored values for the molar volume and entropy of solids, the free energies of H₂O and CO₂, and the free energies of formation for 110 geologically-important phases. P-T-X _{CO 2} calculations of devolatilization equilibria can be made at pressures from 0.2 through 10 kb, and temperatures from 200 through 1,000° C. P-T-X calculations of solid-solid equilibria may be accomplished at pressures to 30 kb and temperatures to 1,000° C. Calculations can be extrapolations from experimental points, or direct calculations from thermochemical data alone. Options are available in these programs to consider effects of: real vs. ideal gas mixing, thermal expansion and compressibility, solid solution, fluid pressure differing from solid pressure, and uncertainties in high-temperature entropies.A collection of thermodynamic data programs accompanies the programs for calculating P-T-X _{CO 2} equilibria. Over a wide range of physical conditions, the data functions report free energies, entropies, fugacities of H₂O and CO₂, high temperature entropies of solids, and activities of components in H₂O-CO₂ mixtures.List of Symbols Activity of H₂O and CO₂ - G_f Free energy of formation of a phase from elements - G_r Free energy change of reaction - G _r ^o Standard state free energy change of a reaction - Free energies of pure H₂O and CO₂ - H _r ^o Standard state enthalpy change for a reaction - K Equilibrium constant - R Gas constant - S _r ^o Standard state entropy change of reaction - S _s ^o Standard state entropy change of solids in a reaction - V_s ^o Standard state volume change of a reaction - V_s ^o Standard state volume change of solids in a reaction - Mole fraction of H₂O and CO₂ - Activity coefficient of H₂O and CO₂     

Solubility of CO2 in olivine melilitite at high pressures and role of CO2 in the earth's upper mantle

The positions of the liquidi and the near-liquidus phases of olivine-melilitite+CO₂ have been determined under MH-buffered and furnace-buffered conditions up to 40 kb. It is found that CO₂ alone lowers the liquidus compared to dry conditions, yet its influence is minor compared to H₂O. The major role of CO₂ is to favour the growth of orthopyroxene and garnet over that of olivine at least at high pressures. CO₂-contents of glasses from experiments just above the liquidus (MH-buffered) were determined as 5.1 % at 10kb; 7.5 % at 20kb, 9.3 % at 30kb and 10–11 % (estimated) at 40 kb. Experiments on (pyrolite –40 % olivine)+H₂O+CO₂ show that CO₂ occurs under mantle conditions as carbonate under subsolidus conditions and dissolved in a melt above the solidus. At 30kb, the solidus lies between 1,000 ° C and 1,050 ° C for vapour-saturated conditions, at and at .     

The thermodynamic regime of metamorphism in the ancient subduction zones

Based on mineralogical themometry and baroraetry and computation of mineral reactions modelling metamorphic sequence, a geotherm for metamorphic belts of the subduction zones has been deduced. Relatively low PT-values (3 kbar/200° C) correspond to zeolite and prehnite-pumpellyite metasediments and at higher pressures and temperatures (10 kbar/400 °C) lawsonite-glaucophane assemblages become unstable. The PT-curve achieves maximum at 11 kbar and 470° C to drop down to normal geotherm (Perchuk 1977). High concentration of H₂O in the metamorphic fluid has been revealed, the difference between P_f1 and being less than 2 kbar. Consideration has also been given to specific thermodynamic regime of zeolite and prehnite-pumpellyite zones of the younger island arcs, where lawsoniteglaucophane zones are absent. Here the geotherm has been found to rise from 0.2kbar/120° C up to 4 kbar/350° C and -regime similar to that of glaucophane schists formations.     

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

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

Stable isotope studies of metasomatic Ca-Fe-Al-Si skarns and associated metamorphic and igneous rocks,Osgood Mountains,Nevada

Garnet-pyroxene skarns were formed 90 m.y. B.P. in the Osgood Mountains at or near contacts of grandiorite with calcareous rocks of the Cambrian Preble Formation. The metasomatic replacement followed contact metamorphic recrystallization of the Preble. The sources, temperature, and variation in H₂O/CO₂ ratios of the metasomatic fluid are interpreted from 269 analyses of oxygen, carbon, hydrogen, and sulfur isotopes in whole rocks, minerals and inclusion fluids.Skarns formed in three mineralogical stages. Oxygen isotope data indicate that temperatures during the crystallization of garnet, pyroxene and wollastonite (Stage I) were least 550 ° C, and that the metasomatic fluid had an 0.035 in the massive skarns, and 0.12 in vein skarns up to 3 cm thick. Pore fluids in isotopic equilibrium with garnet in calc-silicate metamorphic rocks, on the other hand, had 0.15.The metasomatic fluids of Stage I were derived primarily from the crystallizing magma. The isotopic composition of magmatic water was ¹⁸O =+9.0, D= –30 to –45. Oxygen isotope temperatures of greater than 620 ° C were determined for the granodiorite. Isotopic and chemical equilibria between mineral surfaces and the metasomatic fluid were approached simultaneously in parts of the skarn several meters or more apart, while isotopic and chemical disequilibria (i.e. zoning) have been preserved between 20 to 40 m-thick zones in grandite garnet. More Fe-, or andradite-rich garnet crystallized in more H₂O-rich C-O-H fluids ( 0.01) than present with grossularite-rich garnet ( 0.035).Stage II was marked by the replacement of garnet and pyroxene by quartz, amphibole, plagioclase, epidote, magnetite, and calcite. Many of the replacement reactions took place over a relatively narrow range in temperature (480–550 ° C), as indicated by ¹⁸O fractionations between quartz and amphibole. Meteoric water comprised 20 to 50% of the metasomatic fluid during Stage II.Calcite was formed along with pyrite, minor pyrrhotite, and chalcopyrite during Stage III, although the crystallization of pyrite and calcite had begun earlier, during Stages I and II, respectively. Carbon and sulfur isotope compositions of calcite and pyrite indicate a magmatic source for most of the C and S in the metasomatic fluids of Stage III. By the end of Stage III, meteoric water constituted as much as 100% of the metasomatic fluid. Minerals from grandiorite and skarn do not show large depletions in ¹⁸O because the oxygen isotope composition of the metasomatic fluid was buffered by the calcareous wall rocks and the grandiorite.Meteoric water in the vicinity of the Osgood Mountains during the Late Crectaceous (¹⁸O_cale. –14.0, D = – 107) was slightly enriched in ¹⁸O and D relative to present-day meteoric water (¹⁸O = 15.9, D = – 117)