Heat capacity,entropy, and phase equilibria of dmitryivanovite

The heat capacity (C _p ) of dmitryivanovite synthesized with a cubic press was measured in the temperature range of 5–664 K using the heat capacity option of a physical properties measurement system and a differential scanning calorimeter. The entropy of dmitryivanovite at standard temperature and pressure (STP) was calculated to be 110.1 ± 1.6 J mol⁻¹ K⁻¹ from the measured C _p data. With the help of new phase equilibrium experiments done at 1.5 GPa, the phase transition boundary between krotite and dmitryivanovite was best represented by the equation: P (GPa) = −2.1825 + 0.0025 T (K). From the temperature intercept of this phase boundary and other available thermodynamic data for krotite and dmitryivanovite, the enthalpy of formation and Gibbs free energy of formation of dmitryivanovite at STP were calculated to be −2326.7 ± 2.1 and −2,208.1 ± 2.1 kJ mol⁻¹, respectively. It is also inferred that dmitryivanovite is the stable CaAl₂O₄ phase at STP and has a wide stability field at high pressures whereas the stability field of krotite is located at high temperatures and relatively low pressures. This conclusion is consistent with natural occurrences (in Ca–Al-rich inclusions) of dmitryivanovite and krotite, where the former is interpreted as the shock metamorphic product of originally present krotite.     

Heat capacity,entropy and phase equilibria of stishovite

The low-temperature heat capacity (C _P) of stishovite (SiO₂) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol⁻¹ K⁻¹, which is considerably smaller (by 2.86 J mol⁻¹ K⁻¹) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).     

Contact metamorphic P–T–t paths from Sm–Nd garnet ages, phase equilibria modelling and thermobarometry: Garnet Ledge, south-eastern Alaska, USA

Sm–Nd garnet‐whole rock geochronology, phase equilibria, and thermobarometry results from Garnet Ledge, south‐eastern Alaska, provide the first precisely constrained P–T–t path for garnet zone contact metamorphism. Garnet cores from two crystals and associated whole rocks yield a four point isochron age for initial garnet growth of 89.9 ± 3.6 Ma. Garnet rims and matrix minerals from the same samples yield a five point isochron age for final garnet growth of 89 ± 1 Ma. Six size fractions of zircon from the adjacent pluton yield a concordant U–Pb age of 91.6 ± 0.5 Ma. The garnet core and rim, and zircon ages are compatible with single‐stage garnet growth during and/or after pluton emplacement. All garnet core–whole rock and garnet rim‐matrix data from the two samples constrain garnet growth duration to ≤5.5 my. A garnet mid‐point and the associated matrix from one of the two garnet crystals yield an age of 90.0 ± 1.0 Ma. This mid‐point result is logically younger than the 90.7 ± 5.6 Ma core–whole rock age and older than the 88.4 ± 2.5 Ma rim‐matrix age for this sample. A MnNaCaKFMASH phase diagram (P–T pseudosection) and the garnet core composition are used to predict that cores of garnet crystals grew at 610 ± 20 °C and 5 ± 1 kbar. This exceeds the temperature of the garnet‐in reaction by c. 50 °C and is compatible with overstepping of the garnet growth reaction during contact metamorphism. Intersection of three reactions involving garnet‐biotite‐sillimanite‐plagioclase‐quartz calculated by THERMOCALC in average P–T mode, and exchange thermobarometry were used to estimate peak metamorphic conditions of 678 ± 58 °C at 6.1 ± 0.9 kbar and 685 ± 50 °C at 6.3 ± 1 kbar, respectively. Integration of pressure, temperature, and age estimates yields a pressure‐temperature‐time path compatible with near isobaric garnet growth over an interval of c. 70 °C and c. 2.3 my.     

Thermochemical redox equilibria of ZoBell's solution

The redox potential of ZoBell's solution, consisting of $\text{3.33 × 10}{}^{\mathrm{?3}}$ molar K₄Fe(CN)₆, $\text{3.33 × 10}{}^{\mathrm{?3}}$ molar K₃Fe(CN)₆ and 0.10 molar KCl, has been measured by a polished platinum electrode vs a saturated KCl, Ag/AgCl reference electrode. Measurements in the temperature range 8–85°C fit the equation $\text{E(}\text{volts}\text{) = 0.23145 ? 1.5220 × 10}{}^{\mathrm{?3}}\text{(t ? 25) ? 2.2449 × 10}{}^{\mathrm{?6}}\text{(t ? 25)}{}^2$ where $\text{t}$ is in degrees Celsius. Evaluation of literature data was necessary to obtain a reliable value for the Ag/AgCl half-cell reference potential as a function of temperature. Combining the measurements from this study with the literature evaluation of the Ag/AgCl reference potential yields the temperature dependent potential for ZoBell's solution: $\text{E(}\text{volts}\text{) = 0.43028 ? 2.5157 × 10}{}^{\mathrm{?3}}\text{(t ? 25) ? 3.7979 × 10}{}^{\mathrm{?6}}\text{(t ? 25)}{}^2$ relative to the standard hydrogen potential. From these data the enthalpy, entropy, free energy and heat capacity for the ferro-ferricyanide redox couple have been calculated. The temperature equation for the potential of ZoBell's solution may be used for checking potentiometric equipment in the determination of the redox potential of natural waters.     

Olivine-melt and orthopyroxene-melt equilibria

The use of non-regular solution models for silicate melts allows saturation temperatures to be calculated with an accuracy of±10 K for Mg and Fe, olivine or orthopyroxene components; and±20 K for Mn, Co and Ni components. This accuracy is comparable to that of the temperature measurement in the experiments with which the models are calibrated. The errors in the temperature calculation are less than a third of those associated with a regular solution model of mineral-melt equilibria. The values of thermodynamic properties predicted by these empirical solution models are larger than those found calorimetrically, but provide a better fit to the existing experimental data. The calculation of thermochemical properties of olivine and orthopyroxene species in both the crystalline and melt phases allows the calculation of mineral-melt s; the values calculated are within one standard error of those reported in the literature. Eruption temperatures calculated from the composition of Hawaiian tholeiite glasses range from 1135 to 1185°C, and are comparable to measured lava temperatures. These temperatures are lower than those calculated for Atlantic MORB confirming that extensive fractional crystallisation has occurred.     

Rutile/TiO<Subscript>2</Subscript>II phase equilibria

The transition between rutile and α-PbO₂ structured TiO₂ (TiO₂II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO₂II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO₂II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO₂II requires formation pressures considerably higher than the graphite–diamond phase boundary.     

Mesozoic to Cenozoic tectono‐metamorphic history of the South Pamir–Hindu Kush (Chitral,NW Pakistan): Insights from phase equilibria modelling,and garnet–monazite petrochronology

The Karakoram–Hindu Kush–Pamir and adjacent Tibetan plateau belt comprise a series of Gondwana‐derived crustal fragments that successively accreted to the Eurasian margin in the Mesozoic as the result of the progressive Tethys ocean closure. These domains provide unique insights into the thermal and structural history of the Mesozoic to Cenozoic Eurasian plate margin, which are critical to inform the initial boundary conditions (e.g. crustal thickness, structure and thermo‐mechanical properties) for the subsequent development of the large and hot Tibetan–Himalaya orogen, and the associated crustal deformation processes. Using a combination of microstructural analyses, thermobarometry modelling and U–Th–Pb monazite and Lu–Hf garnet geochronology, the study reappraises the metamorphic history of exposed mid‐crustal metapelites in the Chitral region of the South Pamir–Hindu Kush (NW Pakistan). This study also demonstrates that trace elements in monazite (especially Y and Dy), combined with thermodynamical modelling and Lu–Hf garnet dating, provides a powerful integrated toolbox for constraining long‐lived and polyphased tectono‐metamorphic histories in all their spatial and temporal complexity. Rocks from the Chitral region were progressively deformed and metamorphosed at sub‐ and supra‐solidus conditions through at least four distinct episodes from the Mesozoic to the Cenozoic. Rocks were first metamorphosed at ~400–500°C and ~0.3 GPa in the Late Triassic–Early Jurassic (210–185 Ma), likely in response to the accretion of the Karakoram during the Cimmerian orogeny. Pressure and temperature subsequently increased by ~0.3 GPa and 100°C in the Early‐ to Mid Cretaceous (140–80 Ma), coinciding with the intrusion of calcalkaline granitic plutons across the Karakoram and Pamir regions. This event is interpreted as the record of crustal thickening and the development of a proto‐plateau within the Eurasian margin due to a long‐lived episode of slab flattening in an Andean‐type margin. Peak metamorphism was reached in the Late Eocene–Early Oligocene (40–30 Ma) at conditions of 580–600°C and ~0.6 GPa and 700–750°C and 0.7–0.8 GPa for the investigated staurolite schists and sillimanite migmatites respectively. This crustal heating up to moderate anatexis likely resulted in the underthrusting of the Indian plate after a NeoTethyan slab‐break off or to the Tethyan Himalaya–Lhasa microcontinent collision and subsequent oceanic slab flattening. Near‐isothermal decompression/exhumation followed in the Late Oligocene (28–23 Ma) as marked by a pressure decrease in excess of ~0.1 GPa. This event was coeval with the intrusion of the 24 Ma Garam Chasma leucogranite. This rapid exhumation is interpreted to be related to the reactivation of the South Pamir–Karakoram suture zone during the ongoing collision with India. The findings of this study confirm that significant crustal shortening and thickening of the south Eurasian margin occurred during the Mesozoic in an accretionary‐type tectonic setting through successive episodes of terrane accretions and probably slab flattening, transiently increasing the coupling at the plate interface. Moreover, they indicate that the south Eurasian margin was already hot and thickened prior to Cenozoic collision with India, which has important implications for orogen‐scale strain‐accommodation mechanisms.     

Pyroxene-melt equilibria

Using a literature survey of analyses of high-Ca pyroxene and co-existing silicate melt pairs and analyses of low-Ca pyroxene-silicate melt pairs, we have performed a thermodynamic analysis of pyroxene-melt equilibria. Three sets of mixing model pairs have been considered, based on two mixing models for liquid silicate solutions and two for pyroxene solid solutions. A modified version of a model developed by Bottinga and Weill (1972) for the mixing properties of silicate melts, in which the melt is considered to be composed of independent network-forming and network-modifying quasi-lattices, more successfully accounts for variations in melt composition than does a model which considers the melt to be composed of simple oxides which mix ideally. An empirical model for the mixing properties of pyroxenes, in which the M1 and M2 sites are considered to be equivalent and are combined as a hypothetical ‘M’ site, is as successful in accounting for variations in pyroxene composition at high temperatures as an ideal multisite mixing model.Using a variety of pyroxene-melt relations, and combinations of the mixing models outlined above, we have developed several pyroxene-melt and low-Ca pyroxene-high-Ca pyroxene geothermometers which have internally-consistent precisions of approximately ±20°C (1σ). One of the two-pyroxene geothermometers has been used to calculate ‘quench’ temperatures for a number of eucrites. Computed temperatures are subsolidus, and are consistent with independent geothermometers and with petrographic observations. The equations may also be used to calculate the composition of pyroxene crystallizing from a silicate melt of known composition, with or without independent knowledge of temperature. Internally consistent precisions vary, but are approximately ± 3 mol% Fs, ± 5 mol% En, and ±4 mol% Wo (all 1σ). These equations may have application in modeling the evolution of mineral compositions during differentiation of basaltic magmas, particularly terrestrial layered intrusions and the lunar magma ocean.     

Modelling of mineral equilibria in ultrahigh-temperature metamorphic rocks from the Anápolis–Itauçu Complex, central Brazil

A new quantitative approach to constraining mineral equilibria in sapphirine‐bearing ultrahigh‐temperature (UHT) granulites through the use of pseudosections and compatibility diagrams is presented, using a recently published thermodynamic model for sapphirine. The approach is illustrated with an example from an UHT locality in the Anápolis–Itauçu Complex, central Brazil, where modelling of mineral equilibria indicates peak metamorphic conditions of about 9 kbar and 1000 °C. The early formed, coarse‐grained assemblage is garnet–orthopyroxene–sillimanite–quartz, which was subsequently modified following peak conditions. The retrograde pressure–temperature (P–T) path of this locality involves decompression across the FeO–MgO–Al₂O₃–SiO₂ (FMAS) univariant reaction orthopyroxene + sillimanite = garnet + sapphirine + quartz, resulting in the growth of sapphirine–quartz, followed by cooling and recrossing of this reaction. The resulting microstructures are modelled using compatibility diagrams, and pseudosections calculated for specific grain boundaries considered as chemical domains. The sequence of microstructures preserved in the rocks constrains a two‐stage isothermal decompression–isobaric cooling path. The stability of cordierite along the retrograde path is examined using a domainal approach and pseudosections for orthopyroxene–quartz and garnet–quartz grain boundaries. This analysis indicates that the presence or absence of cordierite may be explained by local variation in a_H2O. This study has important implications for thermobarometric studies of UHT granulites, mainly through showing that traditional FMAS petrogenetic grids based on experiments alone may overestimate P–T conditions. Such grids are effectively constant a_H2O sections in FMAS‐H₂O (FMASH), for which the corresponding a_H2O is commonly higher than that experienced by UHT granulites. A corollary of this dependence of mineral equilibria on a_H2O is that local variations in a_H2O may explain the formation of cordierite without significant changes in P–T conditions, particularly without marked decompression.     

Phase equilibria of a fluorine-rich leucogranite from the St. Austell pluton,Cornwall

Highly evolved leucogranitic rocks in the St. Austell pluton, Cornwall, of Hercynian age, contain accessory muscovite, topaz and fluorite. We have studied the H₂O-saturated melting behavior of one representative sample. Its solidus and liquidus pass through the points 663 and 725°C, respectively, at 1 kbar, 640 and 665°C at 2 kbar, 610 and 717°C at 4 kbar and 608 and 700+°C at 8 kbar. Plagioclase is on the liquidus at low pressure and topaz is on the liquidus at 4 kbar: The fluorite is consumed in the formation of the first-formed liquid. Calcium can partition into an evolved granitic melt if complexed by fluorine. The fluorite appears to be largely primary in fresh fluorite granite at St. Austell and not to reflect the albitization of oligoclase in the surrounding biotite granite. Such fluorine-rich leucogranites can be expected to be of subsolvus character.     

Analcime equilibria

The stability fields of analcime and analcime+quartz have been investigated using conventional hydrothermal techniques, over the approximate range of conditions 160–600 °C and 500–5000 bars fluid pressure. The dehydration of analcime (Na₂Al₂Si_3·3O_11·6 · nH₂O) to albite, nepheline and H₂O occurs at temperatures of 492±5 °C at 500 bars, 538±5 °C at 1000 bars, 578±5 °C at 2000 bars and 598±5 °C at 3000 bars. In the presence of quartz, analcine dehydrates to highly disordered albite and H₂O at about 200 °C and 2000 bars, 196°±5 °C and 3000 bars, about 190 °C and 4000 bars, and 183±5 °C at 5000 bars P_fluid. The synthetic phase equilibria appear to be compatible with field observations that primary analcimes occur as phenocrysts or in groundmass in some volcanic and hypabyssal rocks and secondary analcimes in sedimentary, hydrothermally altered and low-grade metamorphic rocks.     

Garnet-cordierite-biotite equilibria in the Steinach aureole,Bavaria

Three garnet-biotite pairs and eleven garnet-cordierite-biotite triplets from the Steinach aureole (Oberpfalz, North-East Bavaria) were analyzed using an electron probe microanalyzer.The regional metamorphic muscovite-biotite schists contain garnets strongly zoned with Mn-Ca-rich centers and Fe-rich edges, the average composition being almandine 67 — spessartine 4 — pyrope 4 — grossular (+andradite) 25.The first contact garnet that is formed in mica schists of the outermost part of the aureole is small, virtually unzoned, and has an average composition of almandine 52 — spessartine 37 — pyrope 8 — grossular (+andradite) 3. With increasing metamorphic grade, there is a consistent trend to form garnets richer in Fe ending up with a composition almandine 84.5 — spessartine 5.5 — pyrope 7.5 — grossular (+andradite) 2.5. This trend is accompanied by a general increase in grain size and modal amount of garnet. Associated cordierites and biotites also become richer in Fe with increasing grade. While the garnets in the highest grade sillimanite hornfelses are poorly zoned, the transitional andalusite-sillimanite hornfelses contain garnets with distinct but variable zonation profiles.These facts can possibly be explained by the time-temperature relationships in the thermal aureole. In a phase diagram such as the Al-Fe-Mg-Mn tetrahedron, the limiting mineral compositions of a four-phase volume or a three-phase triangle are fixed by T and P (the latter remaining effectively constant within a thermal aureole). Thus, in garnet-cordierite-biotite assemblages, garnet zonation should be controlled by temperature variation rather than by a non-equilibrium depletion process. Taking into account the experimental data of Dahl (1968), a zoned garnet from a transitional andalusite-sillimanite hornfels would reflect a temperature increase of about 40° C during its growth. A hypothetical P-X diagram is proposed to show semi-quantitatively the compositional variation of garnet-cordierite pairs with varying pressures (T constant).     

P-T-X conditions of calc-silicate formation: evidence from fluid inclusions and phase equilibria; Llano Uplift, central Texas, USA

Abstract The Llano Uplift in central Texas is a Grenville aged (c. 1.1 Ga) metamorphic terrane consisting predominantly of amphibolite facies mineral assemblages. The formation of these assemblages has been attributed to the emplacement of relatively late granite plutons throughout the area. Two types of granitic intrusion have previously been recognized: (1) Town Mountain Granites, which occur as relatively large, circular-shaped bodies of coarse-grained granite, and (2) Younger Granites which are present as smaller and more irregular bodies of finer-grained granite. In the central part of the uplift, wollastonite-bearing calc-silicate rocks occur within the Valley Spring Gneiss. The development of these calc-silicate rocks has been linked to infiltrating fluids presumably derived from spatially associated Younger Granites. The stability of coexisting quartz, calcite, wollastonite, grossular and anorthite and coexisting quartz, calcite, wollastonite, andradite and hedenbergite shows that the calc-silicate rocks equilibrated under H₂O-rich conditions with χCO₂ <0.10. Fluid inclusions present within the calc-silicate minerals are H₂O-rich with salinities of <17 wt% equivalent NaCl. The absence of any detectable CO₂ in the fluid inclusions may indicate entrapment of the inclusions at lower pressures and more H₂O-rich conditions compared to the stability of the peak metamorphic mineral assemblage. Homogenization temperatures, measured for texturally primary inclusions, range from 360 to 368° C corresponding to a density range from 0.53 to 0.82 g/cm³. Isochores for these fluid inclusions, when combined with the stability of the solid-solid equilibria Grs + Qtz = Wo + An, yield formation conditions of 500–550° C at 1–2 kbar. This indicates that the granitic intrusions involved in the formation of the Blount Mountain calc-silicates were emplaced at a pressure of at least 1–2 kbar.     

Metamorphism of ultrahigh‐pressure eclogites from the Kebuerte Valley,South Tianshan,NW China: phase equilibria and P–T path

Eclogites from the Kebuerte Valley, Chinese South Tianshan, consist of garnet, omphacite, phengite, paragonite, glaucophane, hornblendic amphibole, epidote, quartz and accessory rutile, titanite, apatite and carbonate minerals with occasional presence of coesite or quartz pseudomorphs after coesite. The eclogites are grouped into two: type I contains porphyroblastic garnet, epidote, paragonite and glaucophane in a matrix dominated by omphacite where the proportion of omphacite and garnet is >50 vol.%; and type II contains porphyroblastic epidote in a matrix consisting mainly of fine‐grained garnet, omphacite and glaucophane where the proportion of omphacite and garnet is <50 vol.%. Garnet in both types of eclogites mostly exhibits core–rim zoning with increasing grossular (X_gr) and pyrope (X_py) contents, but a few porphyroblastic garnet grains in type I eclogite shows core–mantle zoning with increasing X_py and a slight decrease in X_gr, and mantle–rim zoning with increases in both X_gr and X_py. Garnet rims in type I eclogite have higher X_py than in type II. Petrographic observations and phase equilibria modelling with pseudosections calculated using thermocalc in the NCKMnFMASHO system for three representative samples suggest that the eclogites have experienced four stages of metamorphism: stage I is the pre‐peak temperature prograde heating to the pressure peak (P_max) which was recognized by the garnet core–mantle zoning with increasing X_py and decreasing X_gr. The P–T conditions at P_max constrained from garnet mantle or core compositions with minimum X_gr content are 29–30 kbar at 526–540 °C for type I and 28.2 kbar at 518 °C for type II, suggesting an apparent thermal gradient of ～5.5 °C km^?1. Stage II is the post‐P_max decompression and heating to the temperature peak (T_max), which was modelled from the garnet zoning with increasing X_gr and X_py contents. The P–T conditions at T_max, defined using the garnet rim compositions with maximum X_py content and the Si content in phengite, are 24–27 kbar at 590 °C for type I and 22 kbar at 540 °C for type II. Stage III is the post‐T_max isothermal decompression characterized by the decomposition of lawsonite, which may have resulted in the release of a large amount of fluid bound in the rocks, leading to the formation of epidote, paragonite and glaucophane porphyroblasts. Stage IV is the late retrograde evolution characterized by the overprint of hornblendic amphibole in eclogite and the occurrence of epidote–amphibole facies mineral assemblages in the margins or in the strongly foliated domains of eclogite blocks due to fluid infiltration. The P–T estimates obtained from conventional garnet–clinopyroxene–phengite thermobarometry for the Tianshan eclogites are roughly consistent with the P–T conditions of stage II at T_max, but with large uncertainties in temperature. On the basis of these metamorphic stages or P–T paths, we reinterpreted that the recently reported zircon U–Pb ages for eclogite may date the T_max stage or the later decompression stage, and the widely distributed (rutile‐bearing) quartz veins in the eclogite terrane may have originated from the lawsonite decomposition during the decompression stage rather than from the transition from blueschist to eclogite as previously proposed.     

Phase equilibria and physical properties

The average physical properties of multiphase aggregates, such as rocks, depend on the properties of the individual phases as well as the statistical spatial distribution of the phases, such as the relative concentrations, and the shape, orientation, and distribution of the grains of the individual phases. If the properties of the phases are similar, the aggregate properties depend mainly on volume averages of properties of the phases; this is the case for elastic properties of rocks. If the properties of the phases differ significantly, the geometric distribution of the phases becomes important; this is the case if a fluid phase is present, which may have a large effect on elastic and electrical properties. Laboratory measurements of properties of individual phases and aggregates, used with theoretical treatments of aggregate properties, permits the interpretation of seismic velocities, attenuation and electrical conductivity in the earth in terms of possible compositions, phases and distribution of phases, such as intergranular fluids.     

Granulite facies amphibole and biotite equilibria,and calculated peak-metamorphic water activities

Samples located near the Oregon Dome anorthosite massif in the south-central Adirondack Mountains, New York contain the fluid-buffering mineral assemblages: amphibole + clinopyroxene + orthopyroxene + quartz or biotite + quartz + orthopyroxene + K-feldspar. These rocks were metamorphosed under granulite-facies conditions (T=725°–750°C, P=7.5 kbar) during the Grenville orogeny. The Mg-rich nature of amphiboles, micas, and pyroxenes allow accurate calculation of water activities because corrections for the effects of solid solution are relatively small. The activity of water was low during the peak of granulite-facies metamorphism, with H₂O0.15±0.14. Wollastonite occurrences indicate that the CO₂ was low (<0.3) in nearby rocks, demonstrating that large quantities of CO₂ did not infiltrate in a pervasive manner. The combination of low H₂O with low CO₂ is consistent with the hypothesis that magmatic processes were dominant, generating dry, fluid-absent conditions.Abbreviations fi Fugacity of species i in a fluid - Xi mole fraction of component i in a phase - T temperature - P lithostatic pressure - P _F fluid pressure - _i ^x activity of component i phase X