Experimental tests of garnet peridotite oxygen barometry

We have performed experiments aimed at testing the calibration of oxygen barometers for the garnet peridotite [garnet (Gt)-olivine (Ol)-orthopyroxene (Opx)] phase assemblage. These involved equilibrating a thin layer of garnet sandwiched between layers of olivine and orthopyroxene at 1300°C and 23–35 kbar for 1–7 days. Oxygen fugacity was controlled (but not buffered) by using inner capsules of Fe?Pt alloy or graphitc or molybdenum sealed in welded Pt outer capsules. Post-experiment measurement of fO₂ was made by determining the compositions of Pt-Fe alloy sensors at the interface between garnet and olivine + orthopyroxene layers. The composition of alloy in equilibrium with olivine + orthopyroxene was approached from Fe-oversaturated and Fe-undersaturated conditions in the same experiment with, in general, excellent convergence. Product phase compositions were determined by electron microprobe and a piece of the garnet layer saved for ⁵⁷Fe Mössbauer spectroscopy. The latter gave the Fe³⁺ content of the garnet at the measured P-T-fO₂ conditions. Approach to equilibrium was checked by observed shifts in Fe³⁺ content and by the approach of garnet-olivine Fe?Mg partitioning to the expected value. The compositions of the phases were combined with mixing properties and thermodynamic data to calculate an apparent fO₂ from two possible garnet oxybarometers:- (1) $\begin{gathered} 2Ca_3 Fe_2 Si_3 O_{12} + 2Mg_3 Al_2 Si_3 O_{12} + 4FeSiO_3 = 2Ca_3 Al_2 Si_3 O_{12} \hfill \\ Gt Gt Opx Gt \hfill \\ + 8FeSi_{0.5} O_2 + 6MgSiO_3 + O \hfill \\ Ol Opx \hfill \\ \end{gathered} $ and (2) $\begin{gathered} 2Fe_3 Fe_2 Si_3 O_{12} = 8FeSi_{0.5} O_2 + 2FeSi_3 O_2 \hfill \\ Gt Ol Opx \hfill \\ \end{gathered} $ Comparison of calculated fO₂s with those measured by the Pt-Fe sensors demonstrated that either barometer gives the correct answer within the expected uncertainty. Data from the first (Luth et al. 1990) has an uncertainty of about 1.6 logfO₂ units, however, while that from equilibrium (2) (Woodland and O'Neill 1993) has an error of +/- 0.6 log units, comparable to that of the spinel peridotite oxybarometer. We therefore conclude that equilibrium (2) may be used to calculate the fO₂ recorded by garnet peridotites with an uncertainty of about +/- 0.6 log units, providing the potential to probe the oxidation environment of the deep continental lithosphere. Preliminary application based on data from Luth et al. (1990) indicates that garnet peridotite xenoliths from Southern Africa record oxygen fugacities about 3.0 log units below the FMQ (fayalite-magnetite-quartz) buffer. These are substantially more reducing conditions than those recorded by continental spinel lherzolites which typically give oxygen fugacities close to FMQ (Wood et al. 1990).     

From the simplest chemical system to the natural one: garnet peridotite barometry

The available experimental data on garnet-bearing-assemblages for synthetic chemical systems (MAS, FMAS, CMAS) have been used to calibrate consistent models for the Al-solubility in orthopyroxene coexisting with garnet, on the basis of equilibrium reaction Py(opx) ? Py(gt). The alternative reaction En(opx)+MgTs(opx) ? Py(gt) is discarded as it yields larger a-posteriori uncertainties. To provide a reliable equation, directly applicable to natural garnet lherzolites, each successive synthetic-system calibration is tested against Mori and Green's (1978) natural-system reequilibration data. For the MAS system, an ideal solution model with constant ΔH°, ΔV° and ΔS° based on 12-oxygen structural formulae for aluminous pyroxenes yields the best fit (GPa, K), $${\text{25,134 + 9,941 }}P - 23.177{\text{ }}T{\text{ + }}RT{\text{ ln (}}X_{{\text{Al}}}^{TB'} {\text{) = 0}}$$ . The MAS synthetic-system calibration can be directly applied to the FMAS system by adding an empirical correction term (20,835 [X _Fe ^gt ]²) independent of either pressure and temperature. However, this correction term is not important because of the limited Fe content of mantle peridotites. When calcium is added to the MAS system, the equilibrium constant is calculated as: $$K_{{\text{CMAS}}} = {{[(1 - X_{{\text{Ca}}}^{M2} )^2 (X_{{\text{Al}}}^{TB'} )]} \mathord{\left/ {\vphantom {{[(1 - X_{{\text{Ca}}}^{M2} )^2 (X_{{\text{Al}}}^{TB'} )]} {[(1 - X_{{\text{Ca}}}^X )^3 (X_{{\text{Al}}}^Y )^2 ]}}} \right. \kern-\nulldelimiterspace} {[(1 - X_{{\text{Ca}}}^X )^3 (X_{{\text{Al}}}^Y )^2 ]}}$$ where M2 and TB′ are pyroxene sites and X and Y are garnet sites. Up to 5 GPa, X _Ca ^X ～ and the CMAS experimental data agree well with the MAS model, but for Yamada and Takahashi's (1983) higher pressure experiments (up to 10 GPa), this no longer holds. Indeed, the garnet solid solution does not behave ideally and an asymmetric regular solution model is needed for application to the deepest natural samples available (>7GPa). Calibration based on new high pressure data yields, $$\begin{gathered} \Delta G_{{\text{CMAS}}}^{XS} = (X_{{\text{Ca}}}^X )(1 - X_{{\text{Ca}}}^X )(0.147 - X_{{\text{Ca}}}^X ) \hfill \\ {\text{ }} \cdot {\text{(6,440,535 - 1,490,654 }}P{\text{)}} \hfill \\ \end{gathered}$$ . According to tests of the inferred solution model, the CFMAS system is a good analogue of natural systems in the pressure, temperature and composition ranges covered by the natural-system reequilibration data (up to 1,500° C and 4 GPa). Simultaneous application of this thermobarometer and of the two-pyroxene mutual solubility thermometer (Bertrand and Mercier 1985) to the phases of the garnet-peridotite xenoliths from Thaba Putsoa, Lesotho, yields a refined paleogeotherm for southern Africa strongly contrasting with previous results. The “granular” nodules yield a thermal gradient of about 8 K/km characteristic of a lithospheric-type environment, whereas the “sheared” ones show a lower gradient of about 1 K/km. This is a typical geotherm expected for a steady thermal state with an inflexion point at the depth of about 160 km corresponding to the lithosphere/asthenosphere boundary.     

Scaling of thermodynamic mixing properties in garnet solid solutions

 The volumes and enthalpies of mixing, ΔV ^Mix and ΔH ^Mix, of binary solid-solution aluminosilicate garnets have been studied by computer simulation. The use of “average atoms” to simulate solid solution was found to give results that are considerably different from those obtained by calculating and averaging over many configurations of cations at a given composition. Although we expect mineral properties calculated from model calculations to be correct only on a qualitative rather than a quantitative scale, fair agreement with experiment was obtained where carefully tested potential parameters were used. The results show that mixing behaviour in these materials is controlled by local strain and relaxation effects resulting from the atomic size mismatch of the mixing divalent cations. In particular, ΔV ^Mix and ΔH ^Mix are shown to scale quadratically with the volume difference between the end members, and to vary essentially symmetrically with composition, with a moderate dependence on the degree and nature of cation order. We conclude that computer modelling should be useful in providing detailed qualitative information about the mixing properties of solid solutions, which can help to better constrain and interpret experimental results. Received: 8 March 2000 / Accepted: 1 October 2000     

The biotite isograd, Central Pyrenees: a deformation-controlled reaction

The biotite isograd reaction in Cambro–Ordovician pelites from the Garonne dome in the Central Pyrenees involves the production of biotite at the expense of chlorite, and the gradual reduction in the celadonite (Si) content of individual white micas. The mineral assemblages in the biotite-bearing rocks in the Melles area retain abundant evidence of chemical disequilibrium, due to the sluggish nature of major element diffusion within the white micas. The progress of the isograd reaction is strongly controlled by the progressive development of regional Variscan fabrics, and chemical exchange in the white micas in these metamorphic conditions is only possible during active deformation. Chemical resetting of the white micas takes place via the development of compositional zoning in the deforming micas; this probably occurs as a consequence of the introduction of defects and dislocations, causing more efficient diffusion within parts of individual grains. In the absence of deformation, this biotite isograd reaction would take place at significantly higher temperature and be controlled by the relatively high closure temperature of major element diffusion in white micas. Thus, assigning thermal significance to such continuous isograd reactions is impossible without independent constraints: kinetic factors such as deformation may be the dominant influence in many cases, not the thermodynamic controls.     

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.     

Simulation of thermodynamic mixing properties of garnet solid solutions at high temperatures and pressures

We present results of high temperature, high pressure atomistic simulations aimed at determining the thermodynamic mixing properties of key binary garnet solid solutions. Computations cover the pressure range 0–15 GPa and the temperature range 0–2000 K. Through a combination of Monte-Carlo and lattice-dynamics calculations, we derive thermodynamic mixing properties for garnets with compositions along the pyrope–almandine and pyrope–grossular joins, and compare these with existing experimental data. Across the pressure–temperature range considered, simulations show virtually ideal mixing behaviour in garnet on the pyrope–almandine join, while large excess volumes and enthalpies of mixing are predicted for garnet along the pyrope–grossular join. Excess heat capacities and entropies are also examined. These simulations shed additional light on the link between the behaviour at the atomic level and macroscopic thermodynamic properties: we illustrate the importance of certain atomistic Ca–Mg contacts in the pyrope–grossular solid solutions. For simulation techniques of this type to become sufficiently accurate for direct use in geological applications such as geothermobarometry, there is an urgent need for improved experimental determinations of several key quantities, such as the enthalpies of mixing along both joins.     

Hornblende barometry of the Galway batholith,Ireland: an empirical test

Summary The application of four hornblende geobarometers, two empirical and two experimental, to the 400 Ma Galway Granite, Ireland gives a pressure of crystallization of the zoned hornblende cores in the western parts of the granite of 2.62 ± 1.2 kb falling to < 1.53 ±1.02 kb at the hornblende rims whereas in the more eastern part of the batholith the value of 4.30 ± 0.70 kb is obtained from unzoned hornblendes. These results are consistent with field and petrographic evidence which indicates a much deeper level of early crystallization of the granite in the central and eastern area with larger K-feldspar phenocrysts (up to 6 cm). Although some of the uplift is related to late upward faulting, the main uplift of the centre of the granite in the east was due to late magmatic differential slip against the marginal granite which became vertically foliated. In the west the crystallization of hornblende started and completed at lower pressures than in the east with final hornblende crystallization at the limit of the field of igneous hornblende and at depth of < 5 km. Hornblende geobarometry reveals: (1) that different parts of some batholiths crystallized at very different pressures (and therefore depths) and have been juxtaposed at the present level of erosion (2) that at least the early part of the crystallization of some granites took place at significantly greater depths than the final crystallization and emplacement position; (3) in zoned hornblendes crystallization occurred during magma movement.

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Hornblende-Barometrie des Galway-Batholithen, Irland: Ein empirischer Test

Zusammenfassung Vier Hornblende-Geobarometer, zwei empirische and zwei experimentelle wurden auf den 400 m.y. alten Galway-Granit, Irland, angewendet and ergeben ähnliche Resultate. Der Durchschnitt der Berechnungen gibt einen Kristallisationsdruck der zonierten Hornblendekerne in den westlichen Teilen des Granits von 2.62 ± 1.2 kbar. Diese Werte fallen auf weniger als < 1.53 ± 1.02 kbar in den Hornblenderändern, während in den östlichen Teilen des Batholithen ein Wert von 4.30 ± 0.70 kbar von nicht zonierten Hornblenden erhalten wurde. Diese Ergebnisse stimmen gut mit Geländebeobachtungen und petrographischen Daten überein, die darauf hinweisen, daß der Granit im zentralen und östlichen Bereich in größerer Tiefe kristallisiert ist. Dabei erreichten K-Feldspat Kristalle Maximumlängen von 6 cm, verglichen mit nur 3 cm im Westen und am Rand. Obwohl ein Teil der Hebung auf späte Verwerfungen zurückgeht, war die Haupthebung zentraler Teile des Granites im Osten durch spätmagmatische, differentielle Gleitung gegenüber den randlichen Granitzonen bedingt, wobei letztere vertikal gefältelt wurden. Im Westen begann die Kristallisation der Hornblende bei niedrigeren Drucken als im Osten, wobei die späteste Hornblende-Kristallisation an der Grenze des Feldes magmatischer Hornblende und in Tiefe von < als 5 km stattfand. Hornblende-Geobarometrie zeigt, daß 1. verschiedene Teile des gleichen Batholithen unter verschiedenen Drucken (und somit in verschiedenen Tiefen) kristallisierten und erst im gegenwärtigen Erosions-Niveau nebeneinander gestellt wurden; 2. daß wenigstens die Frühkristallisation einiger Granite in signifikant größeren Tiefen als die Endkristallisation, und die Position der Platznahme lagen; 3. in zonierten Hornblenden Kristallisation während magmatischer Bewegung stattfand.

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With 2 Figures

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Formerly Oum-toub, Skikda, BP56, 21450, Algeria     

Diffusion in garnet: a review

With improvements on high-pressure experimental techniques in multi-anvil apparatus and the development of new analytical tools, major progress has been made on diffusion in garnets in the past several decades. The data obtained in the experimental determination of diffusion coefficients in garnets are of fundamental importance for diffusion modeling and timescales of geological and planetary processes. In this review, we have compiled experimental data on self-diffusion (Si, O, cations), trace element diffusion (Li, Y, Ga, Cr, Sr, REEs), and interdiffusion (Ca–Fe/Mg, Si–Al) in garnet in the light of new advances and recent applications. In addition, some empirical relationships among diffusion parameters (pre-exponential factor D ₀, activation energy E, ionic radius) are also discussed. We hope that this review can provide a useful data digest and guide to future study of diffusion in garnet.     

Duration of Eo-Alpine metamorphic events obtained from multicomponent diffusion modeling of garnet: a case study from the Eastern Alps

Rocks from the Micaschist–Marble Complex of the Wölz Tauern, which are part of the middle Austroalpine unit, contain large (up to 2 cm) garnet crystals that show clear evidence of multistage growth. Isotopic dating indicates that a Variscan (～270 Ma) garnet core was overgrown by new garnet formed during Eo-Alpine metamorphism at Cretaceous times. P-T paths for the Eo-Alpine metamorphism were obtained using the method of pseudosections (Powell and Holland in Metam Geol 16:309–343, 1998) and are consistent with earlier results from independent thermobarometry. Due to the large size of the garnets, growth zoning was preserved during amphibolite facies metamorphism at both Variscan and Alpine times. Full multicomponent diffusion modeling of compositional zoning at the interface of the Alpine and Pre-Alpine garnets in conjunction with the retrieved P-T paths allow average subduction/exhumation as well as heating/cooling rates to be retrieved. The modeling suggests that a minimum subduction/exhumation rate of ～4 cm/a and heating/cooling rates on the order of 100–260°C/Ma for a 60°C subduction angle are required to preserve the observed compositional zoning overall while modifying the zoning at the interface between two garnets to the extent observed. Such rapid rates of burial/exhumation are consistent with the results of direct GPS measurements of convergence rates at several orogenic belts as well as with inferred rates from modeling in the Alps and other areas. In combination, this indicates that such rapid rates are commonplace during metamorphism in collisional orogens and places important constraints on the rheological behavior of crustal blocks in such orogens.     

Towards a Better Understanding of the Fibrolite Problem: the Effect of Reaction Overstepping and Surface Energy Anisotropy

Trachytes from the Euganean Hills District (Italy) contain metapeliticxenoliths that have been pyrometamorphosed during incorporationin the melt. In xenoliths containing sillimanite crystallizedduring a previous regional HT/LP metamorphism, fibrolite systematicallynucleates at the grain boundaries of sillimanite prisms andwithin plagioclase crystals. Ternary feldspar thermometry showsthat plagioclase in contact with sillimanite plots along the750°C solvus that reflects near-equilibrium conditions ofregional metamorphism. Plagioclase containing fibrolite plotscloser towards the 950°C solvus, reflecting the tendencyof plagioclase to re-equilibrate at high temperature duringpyrometamorphism by a fibrolite-forming reaction:     

Shock metamorphism and shock barometry at a complex impact structure: Slate Islands, Canada

The Slate Islands archipelago is believed to represent the central uplifted portion of a complex impact structure. Planar microstructures in quartz and feldspars and shock vitrification of rocks are the most common shock metamorphic features encountered. No diaplectic quartz was identified in the exposed rocks, but minor maskelynite is present. Shatter cones occur on all islands of the archipelago suggesting minimum pressures of 4 ± 2 GPa. The relative frequency of low index planar microstructures of specific, optically determined crystallographic orientations in quartz are correlated with results from shock barometric experiments to estimate peak shock pressures experienced by the exposed target rocks. In general, there is a decrease in shock pressure recorded in the target rocks from about 20–25 GPa in east-central Patterson Island to about 5–10 GPa at the western shore of this island and on Mortimer Island. The shock attenuation gradient is ∼4.5 GPa/km across this section of the island group. However, the shock attenuation has a roughly concentric plan only over the western part of the archipelago. There is no distinct shock center and there are other deviations from circularity. This is probably the result of: (1) the shock wave not having expanded from a point or spherical source because of the ∼1. 0 to 1.5 km size of the impactor; (2) differential movement of large target rock blocks during the central uplift and crater modification phases of the impact process. The orientation of planar deformation features in quartz appears to be independent of the shock wave direction suggesting that crystal structure exerts the primary control on microstructure development. Based on the results of XRD analyses, residual, post-impact temperatures were high enough to cause annealing of submicroscopic damage in shocked quartz. Received: 15 July 1997 / Accepted: 6 October 1997     

Melts of garnet lherzolite: experiments, models and comparison to melts of pyroxenite and carbonated lherzolite

Phase equilibrium experiments on a compositionally modified olivine leucitite from the Tibetan plateau have been carried out from 2.2 to 2.8 GPa and 1,380–1,480 °C. The experiments-produced liquids multiply saturated with spinel and garnet lherzolite phase assemblages (olivine, orthopyroxene, clinopyroxene and spinel ± garnet) under nominally anhydrous conditions. These SiO₂-undersaturated liquids and published experimental data are utilized to develop a predictive model for garnet lherzolite melting of compositionally variable mantle under anhydrous conditions over the pressure range of 1.9–6 GPa. The model estimates the major element compositions of garnet-saturated melts for a range of mantle lherzolite compositions and predicts the conditions of the spinel to garnet lherzolite phase transition for natural peridotite compositions at above-solidus temperatures and pressures. We compare our predicted garnet lherzolite melts to those of pyroxenite and carbonated lherzolite and develop criteria for distinguishing among melts of these different source types. We also use the model in conjunction with a published predictive model for plagioclase and spinel lherzolite to characterize the differences in major element composition for melts in the plagioclase, spinel and garnet facies and develop tests to distinguish between melts of these three lherzolite facies based on major elements. The model is applied to understand the source materials and conditions of melting for high-K lavas erupted in the Tibetan plateau, basanite–nephelinite lavas erupted early in the evolution of Kilauea volcano, Hawaii, as well as younger tholeiitic to alkali lavas from Kilauea.     

Garnet-pyroxene thermometry and barometry in the Scourie granulites,NW Scotland

Garnets and pyroxenes from granulites ranging in composition from trondhjemitic to ultramafic were analysed with the electron probe in order to test current geothermometric and geobarometric models. A consistent pressure and temperature estimate based on garnet-pyroxene equilibria shows that the peak of metamorphism was at $\text{820±50°}\text{C}$ and 11 kb and implies a minimum crustal thickness of 30 km and a maximum geothermal gradient of 25–28°C, km^?1, at 2700 Ma in the Scourie area. These results are in contrast to earlier more extreme P-T estimates of $\text{1150±100°}\text{C and}\text{15±3}\text{kb}$.     

Estimation of the depth of origin of basic magmas: A modified thermodynamic approach and a comparison with experimental melting studies

Thermodynamic calculations, modified after Nicholls et al. (1971), which relate the activity of silica in a lava to the temperature and pressure conditions at which the lava could be in equilibrium with a mantle mineral assemblage, have been extended to H₂O-bearing magmas by using published experimental data to derive the dependence of on the weight fraction of H₂O dissolved in a magma. A petrogenetic grid has been calculated which gives the P-T conditions under which a magma with a given at its liquidus at 1 atm could equilibrate with a mantle mineral assemblage containing olivine (ol) and orthopyroxene (opx) for different amounts of H₂O in the magma at its source. This grid is in good agreement with the results of experimental studies as summarized by Green (1971) and Brey and Green (1975). The results show that the pressure at which a given magma composition can equilibrate with ol + opx increases for increasing amounts of H₂O dissolved in the magma at depth.In addition, experimental data have been used to calculate the effect of olivine crystallization and removal on the in the residual liquid to assess the effect of low-pressure differentiation on . The results show that if 20 % olivine is added to a basalt magma, its calculated pressure of equilibration with ol+opx increases by 4–5 kbar for a given temperature. The calculated effects of olivine removal and H₂O addition on are reasonably consistent with the silicate mixing model of Burnham (1975).Thermodynamic calculations of this type may be useful for assessing the internal consistency of certain experimental data, and in extrapolating the results to other magma compositions. The application of these calculations to determining the possible depth of origin of natural lavas appears to be limited primarily by the difficulty in determining in a lava at its liquidus temperature.