ALBERT

Notes: Abstract The mixing properties of Fe3Al2Si3O12-Ca3Al2Si3O12 garnet solid solutions have been studied in the temperature range 850–1100° C. The experimental method involves measuring the composition of garnet in equilibrium with an assemblage in which the activity of the Ca3Al2Si3O12 component is fixed. Experiments on the assemblage garnet solid solution, anorthite, Al2SiO5 polymorph and quartz at known pressure and temperature fix the activity of the Ca3Al2Si3O12 component through the equilibrium: 1 $$\begin{gathered} {\text{3CaAl}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftarrows {\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} \hfill \\ {\text{Anorthite garnet}} \hfill \\ {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + SiO}}_{\text{2}} \hfill \\ {\text{ sillimanite/kyanite quartz}}{\text{.}} \hfill \\ \end{gathered}$$ This equilibrium, with either sillimanite or kyanite as the aluminosilicate mineral, was used to control $${\text{a}}_{{\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} }^{{\text{gt}}} $$ . The compositions of the garnet solutions produced were determined by measurement of their unit cell edges. At 1 bar Fe3Al2Si3O12-Ca3Al2Si3O12 garnets exhibit negative deviations from ideality at the Fe-rich end of the series and positive deviations at the calcium end. With increasing pressure the activity coefficients for the Ca3Al2Si3O12 component increase because the partial molar volume of this component is greater than the molar volume of pure grossular. Previous studies indicate that the activity coefficients for the Ca3Al2Si3O12 component also increase with increasing (Mg/Mg+Fe) ratio of the garnet. The region of negative deviation from ideality implies a tendency towards formation of a stable Fe-Ca garnet component. Evidence in support of this conclusion has been found in a natural Fe-rich garnet which was found to contain two different garnet phases of distinctly different compositions.

Notes: Abstract Activity coefficients (γ) for grossular in pyrope-grossular garnet have been determined experimentally using the divariant assemblage garnet-anorthite-sillimanite (kyanite)-quartz. Values of γ for garnets with 10–12 mole % grossular have been obtained at 1000 °, 1100 °, 1200 ° and 1300 ° C at pressures between 15 and 21 Kb. The data are consistent with a symmetrical regular solid model for grossular-pyrope solid solutions. The interaction parameter (W) increases linearly with decreasing temperature and is given by W = 7460-4.3 T cals (T in °K). A solvus in the pyrope-grossular solid solution is predicted with a temperature of critical mixing of 629°C±90 ° C.

Notes: Abstract The partitioning of Fe and Mg between coexisting garnet and olivine has been studied at 30 kb pressure and temperatures of 900 ° to 1,400 °C. The results of both synthesis and reversal experiments demonstrate that K D (= (Fe/Mg)gt/(Fe/Mg)OI) is strongly dependent on Fe/Mg ratio and on the calcium content of the garnet. For example, at 1,000 °C/30 kb, K D varies from about 1.2 in very iron-rich compositions to 1.9 at the magnesium end of the series. Increasing the mole fraction of calcium in the garnet from 0 to 0.3 at 1,000 ° C increases K D in magnesian compositions from 1.9 to about 2.5. The observed temperature and composition dependence of K D has been formulated into an equation suitable for geothermometry by considering the solid solution properties of the olivine and garnet phases. It was found that, within experimental error, the simplest kind of nonideal solution model (Regular Solution) fits the experimental data adequately. The use of more complex models did not markedly improve the fit to the data, so the model with the least number of variables was adopted. Multiple linear regression of the experimental data (72 points) yielded, for the exchange reaction: 3Fe2SiO4+2Mg3Al2Si3O12 olivine garnet ⇌ 2Fe2Al2Si3O12+3Mg2SiO4 garnet olivine ΔH ° (30kb) of −10,750 cal and ΔS ° of −4.26 cal deg−1 mol−1. Absolute magnitudes of interaction parameters (W ij ) derived from the regression are subject to considerable uncertainty. The partition coefficient is, however, strongly dependent on the following differences between solution parameters and these differences are fairly well constrained: W FeMg ol -W FeMg gt ≃ 800 cal W CaMg gt -W CaFe gt ≃ 2,670 cal. The geothermometer is most sensitive in the temperature and composition regions where K D is substantially greater than 1. Thus, for example, peridotitic compositions at temperatures less than about 1,300 ° C should yield calculated temperatures within 60 °C of the true value. Iron rich compositions (at any temperature) and magnesian compositions at temperatures well above 1,300 °C could not be expected to yield accurate calculated temperatures. For a fixed K D the influence of pressure is to raise the calculated temperature by between 3 and 6 °C per kbar.

Notes: Abstract Paragneisses of the Ivrea-Verbano zone exhibit over a horizontal distance of 5 km mineralogical changes indicative of the transition from amphibolite to granulite facies metamorphism. The most obvious change is the progressive replacement of biotite by garnet via the reaction: a $${\text{Biotite + sillimanite + quartz }} \to {\text{ Garnet + K - feldspar + H}}_{\text{2}} {\text{O}}$$ which results in a systematic increase in the modal ratio g = (garnet)/(garnet + biotite) with increasing grade. The systematic variations in garnet and biotite contents of metapelites are also reflected by the compositions of these phases, both of which become more magnesian with increasing metamorphic grade. The pressure of metamorphism has been estimated from the Ca3Al2Si3O12 contents of garnets coexisting with plagioclase, sillimanite and quartz. These phases are related by the equilibrium: b $$\begin{gathered} 3 CaAl_2 {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftharpoons Ca_3 Al_2 {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} + 2 Al_2 {\text{SiO}}_{\text{5}} + {\text{SiO}}_{\text{2}} \hfill \\ plagioclase garnet sillimanite quartz \hfill \\ \end{gathered} $$ which has been applied to these rocks using the available data on the mixing properties of plagioclase and garnet solid solutions. Temperature and f H 2O estimates have been made in a similar way using thermodynamic data on the biotite-garnet reaction (a) and the approximate solidus temperatures of paragneisses. Amphibolite to granulite facies metamorphism in the Ivrea-Verbano zone took place in the P-T ranges 9–11 kb and 700–820 °C. The differences in temperature and pressure of metamorphism between g= 0 and g = 1 (5 kms horizontal distance) were less than 50° C and approximately 1 kb. Retrogression and re-equilibration of garnets and biotites in the metapelites extended to temperatures more than 50° C below and pressures more than 1.5 kb below the peak of metamorphism, the degree of retrogression increasing with decreasing grade of the metamorphic “peak”. The pressure and temperature of the peak of metamorphism are not inconsistent with the hypothesis that the Ivrea-Verbano zone is a slice of upthrusted lower crust from the crust-mantle transition region, although it appears that the thermal gradient was too low for the zone to represent a near-vertical section through the crust. The most reasonable explanation of the granulite facies metamorphism is that it arose through intrusion of mafic rocks into a region already undergoing recrystallisation under amphibolite facies conditions.

Notes: Abstract The H2O content of cordierite is often regarded as incidental to its stability, probably because cordierite has substantial fields of stability at low pressures both in wet and dry experimental systems. In this paper we show that, in contrast, the molecular water content of cordierite has profound effects on many equilibria involving this phase. Mg-cordierite has been modelled as an ideal solid solution of the hydrous and anhydrous end-members Mg2Al4Si5O18·1.2H2O and Mg2Al4Si5O18 respectively. The H2O-solubility data of Mirwald and Schreyer (1977) fit this model within experimental uncertainty and yield 1 bar enthalpy and entropy changes for the reaction: $$\begin{gathered} Mg_2 Al_4 Si_5 O_{18} + 1.2H_2 O = Mg_2 Al_4 Si_5 O_{18} \cdot 1.2H_2 O \hfill \\ cordierite fluid codierite \hfill \\ \end{gathered} $$ of −12,300 cal and −32.87 cal/K. This implies that the partial molal entropy of H2O in cordierite at 298 K/l bar is almost exactly the same as the molar entropy of liquid water (16.9 cal/K as opposed to 16.7 cal/K) and that the interaction energy of liquid water with cordierite is only of the order of a few hundred calories per mole. Application of the model to the hydrous experiments of Fawcett and Yoder (1966) and Chernosky (1974) yields a value for ΔG f,298 0 of anhydrous Mgcordierite of between −2,062.71 and −2,074.21 Kcal per mole. This in in good agreement with the calorimetric data of Charlu, Newton and Kleppa (1975) which yield ΔG f,298 0 of −2,067.03±1.18 Kcal. Water pressure has a considerable influence on the (Mg, Fe) isopleths of coexisting cordierite and garnet, and hence, their use as geobarometric curves. Pressures estimated from the Mg/Fe ratios in the high-Mg range can vary by two kilobars or more, depending on the assumed $$P_{H_2 O} $$ , with highest estimates for $$P_{H_2 O} = P_{total} $$ . The stability field of the talc-kyanite “white-schist” assemblage (Schreyer, 1973) is found to expand appreciably as $$P_{H_2 O} $$ is lowered. Thus the minimum pressure required to form this assemblage can be considerably less than the 10 kb required under conditions of $$P_{H_2 O} = P_{total} $$ =P total, as anticipated by Schreyer (1977). The high partial molal entropy of H2O in cordierite results in small entropy changes coupled with large volume changes in dehydration reactions forming cordierite. This greatly influences the slopes and positions of univariant reactions involving cordierite. The stability of cordierite is promoted to higher pressures in H2O-bearing systems where none of the cordierite breakdown products is a hydrate. Cordierite-forming reactions from hydrates can have the H2O released on the relatively low-temperature sides of the reaction curves, an anomalous situation known only in zeolite stability curves. These considerations can have profound effects on model “petrogenetic grids” involving cordierite.