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A calibration is presented for an activity–composition model for amphiboles in the system Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O (NCFMASHO), formulated in terms of an independent set of six end‐members: tremolite, tschermakite, pargasite, glaucophane, ferroactinolite and ferritschermakite. The model uses mixing‐on‐sites for the ideal‐mixing activities, and for the activity coefficients, a macroscopic multicomponent van Laar model. This formulation involves 15 pairwise interaction energies and six asymmetry parameters. Calibration of the model is based on the geometrical constraints imposed by the size and shape of amphibole solvi inherent in a data set of 71 coexisting amphibole pairs from rocks, formed over 400–600 °C and 2–18 kbar. The model parameters are calibrated by combining these geometric constraints with qualitative consideration of parameter relationships, given that the data are insufficient to allow all the model parameters to be determined from a regression of the data. Use of coexisting amphiboles means that amphibole activity–composition relationships are calibrated independently of the thermodynamic properties of the end‐members. For practical applications, in geothermobarometry and the calculation of phase diagrams, the amphibole activity–composition relationships are placed in the context of the stability of other minerals by evaluating the properties of the end‐members in the independent set that are in internally consistent data sets. This has been performed using an extended natural data set for hornblende–garnet–plagioclase–quartz, giving the small adjustments necessary to the enthalpies of formation of tschermakite, pargasite and glaucophane for working with the Holland and Powell data set.  相似文献   
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The production of large volumes of fluid from metabasic rocks, particularly in greenstone terranes heated across the greenschist–amphibolite facies transition, is widely accepted yet poorly characterized. The presence of carbonate minerals in such rocks, commonly as a consequence of sea‐floor alteration, has a strong influence, via fluid‐rock buffering, on the mineral equilibria evolution and fluid composition. Mineral equilibria modelling of metabasic rocks in the system Na2O‐CaO‐FeO‐MgO‐Al2O3‐SiO2‐CO2‐H2O (NCaFMASCH) is used to constrain the stability of common metabasic assemblages. Calculated buffering paths on TXCO2 pseudosections, illustrate the evolution of greenstone terranes during heating across the greenschist‐amphibolite transition. The calculated paths constrain the volume and the composition of fluid produced by devolatilization and buffering. The calculated amount and composition of fluid produced are shown to vary depending on PT conditions, the proportion of carbonate minerals and the XCO2 of the rocks prior to prograde metamorphism. In rocks with an initially low proportion of carbonate minerals, the greenschist to amphibolite facies transition is the primary period of fluid production, producing fluid with a low XCO2. Rocks with greater initial proportions of carbonate minerals experience a second fluid production event at temperatures above the greenschist to amphibolite facies transition, producing a more CO2‐rich fluid (XCO2 = 0.2–0.3). Rocks may achieve these higher proportions of carbonate minerals either via more extensive seafloor alteration or via infiltration of fluids. Fluid produced via devolatilization of rocks at deeper crustal levels may infiltrate and react with overlying lower temperature rocks, resulting in external buffering of those rocks to higher XCO2 and proportions of carbonate minerals. Subsequent heating and devolatilization of these overlying rocks results in buffering paths that produce large proportions of fluid at XCO2 = 0.2–0.3. The production of fluid of this composition is of importance to models of gold transport in Archean greenstone gold deposits occurring within extensive fluid alteration haloes, as these haloes represent the influx of fluid of XCO2 = 0.2–0.3 into the upper crust.  相似文献   
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