Granitoids in the Rozvadov Pluton,Western Bohemia and Oberpfalz

The Rozvadov Pluton is a complex of mainly Variscan granitoid rocks situated near the Bohemian-Bavarian border between Bärnau, Tachov, Rozvadov and Waidhaus, 25 km ESE of the KTB site. Five mappable units can be distinguished, which intruded as folows: (1) slightly deformed leucocratic meta-aplite/metapegmatite dykes with garnet and tourmaline; (2) a complex of cordierite-bearing granitoids, which have been divided into three facies (a) biotite granite with cordierite (at the margin of the complex), (b) biotite-cordierite granite and (c) cordierite tonalite (in the centre of the complex; (3) fine-grained biotite granite of the Rozvadov type with associated pegmatite bodies; (4) two-mica Bärnau granite; and (5) geochemically specialized albite-zinnwaldite-topaz granite (Kríový kámen/Kreuzstein granite) with indications of Sn-Nb-Ta mineralization and associated phosphorus-rich pegmatite cupolas. Rare earth element data suggest that meta-aplite/pegmatite dykes are the result of a batch partial melting process, whereas the compositional variation of the other rock types was mainly controlled by fractional crystallization. The genesis of the cordierite granitoid suite is best explained in terms of a batch melting of metapelitic source followed by crystallization of a cordierite-rich cumulate and K-feldspar enriched melt. The leucocratic pluton constituents — the meta-aplites and the Bärnau and Kíový kámen granites are rich in phosphorus (0.5–0.8%). The main carriers of phosphorus are alkali feldspars, especially K-feldspar (up to 0.8% P₂O₅). The presence of P-rich leucocratic granites is one of the features distinguishing the Variscan granitoids within the Moldanubian zone from the nearly contemporaneous granitoids in the Saxothuringian zone.     

Structural and magnetic properties of Co2Al4Si5O18 and Mn2Al4Si5O18 cordierite

The crystal structures, lattice dynamics and magnetic properties of synthetic Co-cordierite, Co₂Al₄Si₅O₁₈, and Mn-cordierite, Mn₂Al₄Si₅O₁₈ have been studied by neutron powder diffraction, infrared spectroscopy and magnetisation measurements. Due to different synthesis conditions, the Co-cordierite used here crystallised in the hexagonal α-cordierite structure with a disordered Si/Al distribution in the framework, while for the Mn-cordierite the orthorhombic β-structure has been determined. The experimentally determined paramagnetic moments, _exp (Mn) = 5.47(6) _B and _exp (Co) = 3.88(4) _B , are in good agreement with theoretical predictions for octahedrally coordinated Mn²⁺ and Co²⁺, respectively. In both compounds there is no magnetic long-range order down to at least 1.5 K. However, the onset of an anti-ferromagnetic short-range correlation of magnetic moments along [001] has been observed for Mn-cordierite by magnetisation and neutron diffraction measurements. This short-range magnetic correlation becomes evident from diffuse scattering observed at 2 K. The diffuse scattering has been interpreted in terms of a Blech-Averbach function. Received: 30 June 1998 / Revised, accepted: 3 March 1999     

P-T grids for silica-undersaturated granulites in the systems MAS (n+ 4) and FMAS (n+ 3)-tools for the derivation of P-T paths of metamorphism

Abstract Considering the minerals cordierite (Cd), sapphirine (Sa), hypersthene (Hy), garnet (Ga), spinel (Sp), sillimanite (Si) and corundum (Co) in the system FeO-MgO-Al₂O₃-SiO₂ (FMAS), the stable invariant points are [Co], [Ga], [Cd] and [Sa]. Constraints imposed by experimental data for the system MAS indicate that under low P _H2o conditions the invariant points occur at high temperature (> 900° C) and intermediate pressure (7-10 kbar). This temperature is higher than that commonly advocated for granulite facies metamorphism. In granulites Fe-Mg exchange geothermometers may yield temperatures of 100–150° C below peak metamorphic conditions and evidence for peak temperatures is best preserved by relict high-temperature assemblages and by Al-rich cores in orthopyroxene. Application of the FMAS grid to some well-documented granulite occurrences introduces important constraints on their P-T histories. Rocks of different bulk compositions, occurring in close proximity in the field, may record distinct segments of their P-T paths. This applies particularly to rocks with evidence for reaction in the form of coronas, symplectites and zoned minerals. Consideration of curved reaction boundaries and _XMs isopleths may explain apparently contradictory results for the stability of cordierite obtained from low-temperature experiments and thermochemical calculations on the one hand and hightemperature experimental data on the other.     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

Recalibration of mutually consistent garnet–biotite and garnet–cordierite geothermometers

Garnet–biotite and garnet–cordierite geothermometers have been consistently calibrated, using the results of Fe²⁺–Mg cation exchange experiments and utilizing recently evaluated nonideal mixing properties of garnet. Nonideal mixing parameters of biotite (including Fe, Mg, Al^VI, and Ti) and of cordierite (involving Fe and Mg) are evaluated in terms of iterative multiple least-square regressions of the experimental results. Assuming the presence of ferric Fe in biotite in relation to the coexisting Fe-oxide phases (Case A), and assuming the absence of ferric Fe in biotite (Case B), two formulae of garnet–biotite thermometer have been derived. The garnet–cordierite geothermometer was constructed using Margules parameters of garnet adopted in the garnet–biotite geothermometers. The newly calibrated garnet–biotite and garnet–cordierite thermometers clearly show improved conformity in the calculated temperatures. The thermometers give temperatures that are consistent with each other using natural garnet–biotite–cordierite assemblages within ±50 °C. The effects of ferric Fe in biotite on garnet–biotite thermometry have been evaluated comparing the two calibrations of the thermometer. The effects are significant; it is clarified that taking ferric Fe content in biotite into account leads to less dispersion of thermometric results.     

Dehydration process and structural development of cordierite ceramic precursors derived from FTIR spectroscopic investigations

 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H₂O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H₂O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H₂O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm⁻¹ reveals non-bridging and bridging H₂O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm⁻¹ lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm⁻¹ are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm⁻¹ is assigned to stretching modes of AlO₄ tetrahedral units and the same assignment holds for a band at 783 cm⁻¹ which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm⁻¹ and the band at 572 cm⁻¹ is assigned to stretching vibrations of AlO₆ octahedral units. A strong band around 440 cm⁻¹ is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm⁻¹ bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H₂O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002     

Diffusion-controlled biotite breakdown reaction textures at the solid/liquid transition in the continental crust

Two-phase quartz intergrowths with garnet, cordierite and tourmaline occur commonly in prograde high-temperature migmatites, granulites, as well as in the last crystallization stages of biotite granites. Structural, microtextural and mineralogical data show that they result from the breakdown of biotite in the presence of a melt phase associated with incongruent dissolution of feldspars into the melt and silica release (giving quartz in silica saturated rocks). Biotite breakdown and growth of Al-rich ferromagnesian minerals, occurring at the solid–liquid transition in the crust (early melting or final crystallization), is kinetically controlled by Fe and Mg mass transport, the network-forming cations Si and Al being locally compensated for by feldspar dissolution/crystallization. This process leads to significant changes with respect to equilibrium dehydration-melting reactions wherein quartz is a reactant and K-feldspar a reaction product. Therefore, quartz inclusions commonly occurring in garnets from granulite-facies metapelites and metagraywackes are not simply grains passively included during garnet growth. They may also correspond to newly crystallized phases. Resorption of feldspar may lead to more alkaline melt and to crystalline residue richer in Al than expected under equilibrium conditions. Hence, excess alumina in granulite-facies rocks is not necessarily related to initial alumina-rich whole-rock compositions (as currently considered), but may be due, at least partly, to kinetics of melting.     

Cordierite from a high-temperature low-pressure shear zone of the south-western Bohemian Massif (Moldanubian terrain,Austria)

A medium-scale shear zone exposed in the gneiss rocks of the South-western Bohemian Massif (Moldanubian Zone) contains cordierite, whose Na p.f.u. is subject to a significant increase from the centre to the edge of the deformation area, whilst other elements only show negligible variations. Coexisting mineral phases of cordierite include garnet, biotite, and sillimanite. According to the results obtained from the garnet-cordierite Fe²⁺/Mg²⁺-exchange thermometer a decrease of peak temperature from 639 °C in the central mylonite to 593 °C in the marginal mylonite can be observed, which indicates significant shear heating. Lithological pressures were estimated by considering the position of cordierite-forming reactions in the P-T field and the stability of coexisting sillimanite. They are subject to a reduction from 0.35 GPa in the highest deformed mylonite to 0.31 GPa at the margin of the shear zone. According to the results of comprehensive petrographic and mineralogical studies the investigated shear zone underwent a Variscan HT-LP metamorphic event implying the formation of cordierite and an Alpine MT-LP event entailing the rotation and decomposition of the cordierite phase.     

Statistical microanalysis applied to garnet growth zoning and to cordierite fluid content

An analytical study to evaluate quantitatively weak zoning of a garnet from a high-grade kinzigite has been performed with an electron microprobe. The technique consists of the reconstruction of a profile step-by-step by successive analyses performed during relatively long counting times (30 s), along a radial profile of 2,500 μm length. The successive analytical data along this profile are statistically treated by Fisher's test and compared with the χ² values (Pearson's law). These statistical tests were applied to assess microprobe stability and analysis homogeneity, and as a consequence to assure high credibility of the radial variations of the garnet. From core to rim, and for each element, zoning appears as the radial juxtaposition of stationary Poissonian samples. These samples being associated, the garnet appears to be constituted of successive concentric domains with stationary compositions. Different substitutions between Mg, Fe, Mn and Ca are evidenced. Such an analytical approach to chemical zoning can be useful for understanding growth mechanisms, and the possible diffusion reactions with the environment at each growth step. In addition, such a procedure can be used to evaluate accurately the fluid content of cordierite, and to appreciate the nature of the fluids concerned. As an example, the fluid content of a cordierite from a similar high-grade kinzigite has been evaluated.     

P–T–t evolution of spinel–cordierite–garnet gneisses from the Sauwald Zone (Southern Bohemian Massif, Upper Austria): is there evidence for two independent late-Variscan low-P/high-T events in the Moldanubian Unit?

The Sauwald Zone, located at the southern rim of the Bohemian Massif in Upper Austria, belongs to the Moldanubian Unit. It exposes uniform biotite + plagioclase ± cordierite paragneisses that formed during the post-collisional high-T/low-P stage of the Variscan orogeny. Rare metapelitic inlayers contain the mineral assemblage garnet + cordierite + green spinel + sillimanite + K-feldspar + plagioclase + biotite + quartz. Mineral chemical and textural data indicate four stages of mineral growth: (1) peak assemblage as inclusions in garnet (stage 1): garnet core + cordierite + green spinel + sillimanite + plagioclase (An_35–65); (2) post-peak assemblages in the matrix (stages 2, 3): cordierite + spinel (brown-green and brown) ± sillimanite ± garnet rim + plagioclase (An_10–45); and (3) late-stage growth of fibrolite, muscovite and albite (An_0–15) during stage 4. Calculation of the P–T conditions of the peak assemblage (stage 1) yields 750–840°C, 0.29–0.53 GPa and for the stage 2 matrix assemblage garnet + cordierite + green spinel + sillimanite + plagioclase 620–730°C, 0.27–0.36 GPa. The observed phase relations indicate a clockwise P–T path, which terminates below 0.38 GPa. The P–T evolution of the Sauwald Zone and the Monotonous Unit are very similar, however, monazite ages of the former are younger (321 ± 9 Ma vs. 334 ± 1 Ma). This indicates that high-T/low-P metamorphism in the Sauwald Zone was either of longer duration or there were two independent phases of late-Variscan low-P/high-T metamorphism in the Moldanubian Unit.