THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

The Glarus thrust: excursion guide and report of a field trip of the Swiss Tectonic Studies Group (Swiss Geological Society, 14.–16. 09. 2006)

This excursion guide results form a field trip to the Glarus nappe complex organized by the Swiss Tectonic Studies Group in 2006. The aim of the excursion was to discuss old and recent concepts related to the evolution of the Glarus thrust. The major aspects were (i) the interplay between deformation, fluid flow and geochemical alteration, (ii) episodic versus continuous deformation and fluid flow, and (iii) the link between large-scale structures, microstructures, and geochemical aspects. Despite 150 years of research in the Glarus nappe complex and the new results discussed during the excursion, there exist controversies that still are unsolved.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Hydration of periclase at 350 ∘C to 620 ∘C and 200 MPa: experimental calibration of reaction rate

The hydration of periclase to brucite was investigated experimentally. Single crystals of periclase machined to millimeter sized cubes with (100) surfaces were reacted with distilled water at temperatures of 350 to 620 ^°C and a pressure of 200 MPa for run durations of 5 to 40 minutes. Hydration produced a layer of brucite covering the surface of periclase. While the shrinking periclase largely retained its cube shape a surface roughness developed on the μm scale and eventually outward pointing spikes bounded by (111) faces emerged on the retreating faces of the periclase due to kinetic selection of less reactive (111) and (110) surfaces. The periclase to brucite conversion followed a linear rate law, where the reaction rate increased from 350 to 530 ^°C and then decreased towards higher temperature and finally vanished at about 630 ^°C, where periclase, brucite, and water are in equilibrium at 200 MPa. The overall kinetics of the hydration reaction is conveniently described in terms of a phenomenological interface mobility. Measuring the velocity of the hydration front relative to the lattice of the reactant periclase, the temperature dependence of its mobility is described by an Arrhenius relation with pre-exponential factor 1.7.10^?12 m ⁴/s.J and activation energy of E_A=55 kJ/mol.     

Metasomatic coronas around hornblendite xenoliths in granulite facies marble, Ivrea zone, N Italy. II: Oxygen isotope patterns

Up to 20-cm-wide metasomatic reaction bands formed coronas around hornblendite xenoliths in a marble matrix during high grade metamorphism in the Ivrea zone. The coronas are comprised of an innermost monomineralic clinopyroxene layer, a garnet-clinopyroxene layer and an outermost scapolite-clinopyroxene layer. The oxygen isotope composition of the original hornblendite core is 7‰ relative to V-SMOW and the oxygen isotope composition of the marble matrix is 19.7‰. The oxygen isotope transition across the corona is represented by a diffusion front with a step discontinuity at the inner margin of the corona. The systematics of the inter-mineral fractionations indicates preservation of the oxygen isotope compositions from high temperatures and maintenance of grain-scale oxygen isotope equilibrium during corona formation. The oxygen isotope pattern is interpreted in terms of a moving boundary diffusion problem. The growing reaction band and the reactant hornblendite and marble represent a total of five media with different transport properties and moving separation surfaces. Bulk oxygen diffusion was at least three orders of magnitude faster then expected from volume diffusion, suggesting that transport was enhanced by relatively fast diffusion along grain boundaries. Oxygen diffusivities in the individual layers correlate with the oxygen volume diffusivities in the major constituent minerals of the respective layers, suggesting mineralogical control on bulk oxygen diffusion.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.     

Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole

Summary ?The intrusive complex of Monzoni in the western central Dolomites (northern Italy) comprises a suite of pyroxenites, monzogabbros and monzodiorites with solidus temperatures in excess of 1000 °C which intruded previously unmetamorphosed Permotriassic sediments at less than 5 km depth. At the eastern intrusive contact an approximately 860 m wide contact aureole is developed in the carbonate country rocks. The prograde sequence of mineral parageneses in a siliceous dolomite of the Cencenighe member and in marly limestones of the Val Badia and Cencenighe members of the Lower Triassic Werfen formation indicate peak metamorphic temperatures in excess of 698 °C at 185 m from the intrusive contact and an outward temperature decrease of approximately 65 °C per 100 m. The high temperatures in the inner aureole caused formation of periclase from the prograde breakdown of dolomite and formation of melilite and esseneite-rich clinopyroxene. Present address: Mineralogisch-Petrographisches Institut, Universit?t Basel, Switzerland Received April 7, 2001; revised version accepted December 6, 2001     

Silicon and oxygen self diffusion in enstatite polycrystals: the Milke et al. (2001) rim growth experiments revisited

Milke et al. (Contrib Mineral Petrol 142:15–26, 2001) studied the diffusion of Si, Mg and O in synthetic polycrystalline enstatite reaction rims. The reaction rims were grown at 1,000°C and 1 GPa at the contacts between forsterite grains with normal isotopic compositions and a quartz matrix extremely enriched in ¹⁸O and ²⁹Si. The enstatite reaction rim grew from the original quartz-forsterite interface in both directions producing an inner portion, which replaced forsterite and an outer portion, which replaced quartz. Here we present new support for this statement, as the two portions of the rim are clearly distinguished based on crystal orientation mapping using electron backscatter diffraction (EBSD). Milke et al. (Contrib Mineral Petrol 142:15–26, 2001) used the formalism of LeClaire (J Appl Phys 14:351–356, 1963) to derive the coefficient of silicon grain boundary diffusion from stable isotope profiles across the reaction rims. LeClaires formalism is designed for grain boundary tracer diffusion into an infinite half space with fixed geometry. A fixed geometry is an undesired limitation in the context of rim growth. We suggest an alternative model, which accounts for simultaneous layer growth and superimposed silicon and oxygen self diffusion. The effective silicon bulk diffusivity obtained from our model is approximately equal within both portions of the enstatite reaction rim: D _Si,En ^eff =1.0–4.3×10^–16 m² s^–1. The effective oxygen diffusion is relatively slow in the inner portion of the reaction rim, D _O,En ^eff =0.8–1.4×10^–16 m² s^–1, and comparatively fast, D _O,En ^eff =5.9–11.6×10^–16 m² s^–1, in its outer portion. Microstructural evidence suggests that transient porosity and small amounts of fluid were concentrated at the quartz-enstatite interface during rim growth. This leads us to suspect that the presence of an aqueous fluid accelerated oxygen diffusion in the outer portion of the reaction rim. In contrast, silica diffusion does not appear to have been affected by the spatial variation in the availability of an aqueous fluid.

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Perthite microstructure in magmatic alkali feldspar with oscillatory zoning; Weinsberg Granite, Upper Austria

Feldspar megacrysts from the Weinsberg granite (Moldanubian Zone) show oscillatory zoning with respect to the albite- and orthoclase components. All growth zones show perthitic exsolutions which take the form of bleb- and lens shaped albite-rich precipitates in an orthoclase-rich host. The average sizes and shapes of the precipitates show systematic variation with the integrated bulk compositions of the respective growth zones. The precipitates are abundant and relatively small in growth zones with intermediate bulk composition (Or50Ab41An09 - Or80Ab18An02), and they are less abundant and larger in more orthoclase-rich zones (Or88Ab11An01). Small precipitates have a relatively high aspect ratio, whereas the large precipitates in the potassium-rich zones are more spherical. The relation between microstructure and integrated bulk composition suggests that exsolution and subsequent growth and coarsening occurred by different mechanisms in the respective growth zones. Numerical modeling shows that rapid growth of precipitates over extended periods of time and attainment of relatively large final size is favored, if only few nuclei are formed in an oversaturated host. In contrast, precipitates can grow rapidly only over limited time intervals and remain relatively small, if abundant nuclei are present. During cooling of the oscillatorily zoned alkali-feldspar, exsolution started at relatively high temperatures in growth zones of intermediate integrated bulk composition as compared to exsolution in the more orthoclase-rich growth zones. Irrespective of whether exsolution occurred by spinodal decomposition or by nucleation at relatively high temperatures in the growth zones of intermediate integrated bulk composition, it produced abundant nuclei and resulted in relatively small precipitates. In contrast, comparatively few nuclei were formed in the orthoclase-rich growth zones resulting in large precipitates. The Na/K partitioning between precipitates and the host is independent of the integrated bulk composition of the respective growth zone reflecting re-equilibration during cooling down to relatively low temperatures (<?400°C). The shape of the precipitates probably has evolved from an initially lamellar or spindle-like geometry with high aspect ratio to more isometric, spheroidal shapes during precipitate growth and coarsening. Host/precipitate interfaces served as fluid pathways during late stage deuteric alteration.