Structural investigations of the two polymorphs of synthetic Fe-cordierite and Raman spectroscopy of hexagonal Fe-cordierite

The crystal structures of synthetic hexagonal and orthorhombic Fe-cordierite polymorphs with the space groups P6/mcc and Cccm were refined from single-crystal X-ray diffraction data to R _{1, hex}?=?3.14 % and R _{1, ortho}?=?4.48 %. The substitution of the larger Fe²⁺ for Mg leads to multiple structural changes and an increase of the unit cell volumes, with a, c (hex)?=?9.8801(16) Å, 9.2852(5) Å and a, b, c (ortho)?=?17.2306(2) Å, 9.8239(1) Å, 9.2892(1) Å in the end-members. Furthermore Fe incorporation results in an increase of the volumes of the octahedra, although the diameters of the octahedra in direction of the c-axis decrease in both polymorphs. X-ray powder diffraction analysis indicates a high degree of Al/Si ordering in the orthorhombic polymorph, the Miyashiro distortion index is ~0.24. Estimations of site occupancies based on the determined tetrahedral volumes result in the following values for hexagonal Fe-cordierite: ~73 % Al for T₁ and ~28 % Al for T₂. For the first time Raman spectroscopy was performed on the hexagonal Fe-cordierite polymorph. In the hexagonal Fe-cordierite polymorph most Raman peaks are shifted towards lower wavenumbers when compared with the Mg-end-member.     

Corundum-bearing amphibolites from the metamorphic basement of the Krivaja–Konjuh ultramafic massif (Dinaride Ophiolite Zone, Bosnia)

Summary ?Corundum-bearing amphibolites are part of the metamorphic basement of the Krivaja–Konjuh ultramafic massif in the Dinaride Ophiolite Zone in Bosnia. Pinkish corundum occurs as porphyroblasts and together with edenitic–pargasitic hornblende and anorthite within the amphibolites. Based on major and trace element contents, the protoliths of the corundum-bearing amphibolites were tholeiitic gabbro cumulates. Geothermobarometric estimations on the corundum-bearing amphibolites yielded preliminary P–T conditions of 620–830 °C and 6–10 kbar for amphibole and plagioclase inclusions inside corundum and 4.5–8 kbar for the main metamorphic assemblage. These estimates are thought to reflect the metamorphic conditions achieved during the Late Jurassic obduction of the Krivaja–Konjuh ultramafic massif onto ophiolite mélange. This study documents the mineralogy, petrology and geochemistry of these unusual corundum-bearing ophiolite-related edenite–pargasitic amphibolites. Received June 20, 2002; accepted October 22, 2002     

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.     

Metasomatic reaction bands at the Mt. Hochwart gneiss-peridotite contact (Ulten Zone, Italy): insights into fluid-rock interaction in subduction zones

We investigated the contact zone between peridotite lenses and host gneisses located on the northern side of the Hochwart peak, also known as Vedetta Alta (Ulten Zone, Alto Adige -Südtirol) where metasomatic contact bands occur. The country rocks are gneisses consisting mainly of quartz, K-feldspar, garnet, kyanite, biotite and muscovite. The ultramafic body consists of a hectometre-sized garnet peridotite and harzburgite lens. The reaction zone shows mineralogic zoning from phlogopite-rich to tremolite-anthophyllite-talc-rich rocks from the host gneiss towards the peridotite. In some cases, lenses of serpentine and talc in association with chlorite, and trondhjemitic pods develop at the ultramafic rocks border to the gneisses. Trondhjemite dikes with pegmatoid texture also crosscut the peridotite body. Phlogopite aggregates with accessory zircon, Cl-apatite and tourmaline and phlogopite-hornblende aggregates also occur. The combination of petrography, mineral chemistry and mass balance calculations constrains the gains and losses of elements during metasomatism. Reaction zone formation involved extensive addition of H₂O, K₂O and LILE from the fluid, whereas MgO, CaO and Al₂O₃ were removed from the peridotite. Thus, the formation of the reaction zones between the mantle rocks and the gneisses was triggered by considerable fluid/melt circulation, causing crystallisation of mainly phlogopite, anthophyllite and talc, and the release of a trondhjemitic residual melt. Field mapping provides evidence that the internal structures of the host migmatites (folds) and those of the peridotites (foliation, fluid texture) are discordant. Pseudosection calculations give insights into the P-T conditions (T 660–700°C; P 0.5–0.7 GPa) of metasomatism responsible for the formation of reaction zones, which is related to the retrograde path of the Ulten Zone peridotites. Our results suggest that the redistribution of major and trace elements in subduction zones is strongly influenced by metasomatic reactions occurring at the slab-mantle interface.     

Geothermobarometry of Al2SiO5-bearing metapelites in the western Austroalpine Ötztal-basement

Summary The dominant amphibolite-facies Variscan event in the Austroalpine Ötztal basement can best be studied in the northwestern part of the Ötztal block. Further to the southeast it is overprinted by Alpine metamorphism. Metapelites with the assemblage garnet-staurolite-kyanite-sillimanite±andalusite-biotite-muscovite-plagioclase were used to reconstruct pressure and temperature conditions with exchange thermometry, net transfer equilibria and multi-equilibrium methods. Assuming kyanite as equilibrium Al₂SiO₅ polymorph, conditions of 570–640°C and 5.8–7.5kbar are derived using garnet rim compositions. Typical nonequilibrium textures are (1) continuous chemical zoning of garnets, (2) inclusions of kyanite and fibrolite in andalusite porphyroblasts and (3) the spectacular replacement of garnet by fibrolite and biotite. The latter two textures were used to decipher the retrograde part of the P-T path. Application of the differential thermodynamics approach (Gibbs method) indicates prograde garnet growth during pressure release. Addition of CaO to the KFASH-system allows the garnet breakdown within the staurolite stability field and its quantification, using the quartz-garnet-aluminosilicate-muscovite geothermobarometer, revealed temperatures of 530–630°C and 3.5–5.7kbar. Andalusite formation is thought to constrain the final stage of the P-T path. Textural and chemical data clearly indicate a continuous pre-Alpine metamorphic evolution.

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Geothermobarometrie in Al₂SiO₅ führenden Metapeliten des westlichen Ötztal Kristallins

Zusammenfassung Die dominierende variszische Metamorphose im ostalpinen Ötztal Kristallin kann aufgrund der Zunahme der alpidischen Überprägung nach Südosten am besten im nordwestlichen Teil des Ötztal Kristallins untersucht werden. Die Metamorphosebedingungen wurden in den Metapeliten anhand der Paragenese Granat-Staurolith-Kyanit-Sillimanit±Andalusit-Biotit-Muskovit-Plagioklas mit Hilfe von Kationenaustauschthermometrie, kontinuierlichen Mineralreaktionen und der Berechnung aller formulierbaren Mineral-Gleichgewichte durchgeführt. Mit der Annahme von Kyanit als Teil der Gleichgewichtsparagenese wurden Temperaturen von 570–640°C und Drucke von 5.8–7.5kbar für die Granatränder ermittelt. Folgende Ungleichgewichtsphänomene wurden zur Belegung des Metamorphosepfades herangezogen: (1) Kontinuierlicher Granatzonarbau (2) Andalusitporphyroblasten mit Kyanit-und Fibrolitheinschlüssen und (3) die Reaktion von Granat zu Biotit und Fibrolith Pseudomorphosen. Die Anwendung der Gibbs-Methode lässt Rückschlüsse auf ein progrades Granatwachstum bei fallenden Drücken und steigenden Temperaturen zu. Die Erweiterung des KFASH-Systems mit CaO ermöglicht den Granatzerfall noch im Stabilitätsfeld von Staurolith und die Anwendung des Granat-Muskovit-Aluminiumsilikat-Quarz Geothermobarometers belegt den Granatzerfall bei 530–630°C und 3.5–5.7kbar. Die Andalusitkristallisation wird als letztes Stadium des Druck-Temperatur Pfades angenommen. Texturelle und chemische Untersuchungen lassen den Schluss auf eine einphasige variszische Metamorphose zu.

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With 9 Figures     

The metamorphic evolution of migmatites from the Ötztal Complex (Tyrol,Austria) and constraints on the timing of the pre-Variscan high-T event in the Eastern Alps

Within the Ötztal Complex (ÖC), migmatites are the only geological evidence of the pre-Variscan metamorphic evolution, which led to the occurrence of partial anatexis in different areas of the complex. We investigated migmatites from three localities in the ÖC, the Winnebach migmatite in the central part and the Verpeil- and Nauderer Gaisloch migmatite in the western part. We determined metamorphic stages using textural relations and electron microprobe analyses. Furthermore, chemical microprobe ages of monazites were obtained in order to associate the inferred stages of mineral growth to metamorphic events. All three migmatites show evidence for a polymetamorphic evolution (pre-Variscan, Variscan) and only the Winnebach migmatite shows evidence for a P-accentuated Eo-Alpine metamorphic overprint in the central ÖC. The P-T data range from 670–750 °C and < 2.8 kbar for the pre-Variscan event, 550–650 °C and 4–7 kbar for the Variscan event and 430–490 °C and ca. 8.5 kbar for the P-accentuated Eo-Alpine metamorphic overprint. U-Th-Pb electron microprobe dating of monazites from the leucosomes from all three migmatites provides an average age of 441 ± 18 Ma, thus indicating a pervasive Ordovician-Silurian metamorphic event in the ÖC.     

The compositional variation of synthetic sodic amphiboles at high and ultra-high pressures

Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H₂O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H₂O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H₂O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of Al^IV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [Na^AAl^IV]<=>[□^ASi] (edenite) toward nyböite, and [Na^(M4)Al^VI]<=>[Mg^(M4)Mg^VI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.     

U–Pb geochronology of detrital zircons from a contact metamorphic Brixen Quartzphyllite (South-Tyrol, Italy): evidence for a complex pre-Variscan evolution of the Southalpine basement

Laser ablation ICP-MS U–Pb zircon geochronology of detrital zircons from a contact metamorphic sample of the Brixen Quartzphyllite from the innermost part of the contact aureole adjacent to the Brixen granodiorite yielded three different Precambrian concordia ages: zircon cores and an older generation of zircons give a maximum age of 2,023 ± 31 Ma, zircon rims and a younger generation of single grains yield a concordia age of 882 ± 19 Ma. A third generation of single zircon grains yields an age of 638 ± 20 Ma. In contrast to Austroalpine quartzphyllite complexes from the Eastern Alps neither Cambrian/Ordovician (570–450 Ma) nor Carboniferous (360–340 Ma) ages on single zircons have been observed so far in these samples. These ages provide evidence of a complex pre-Variscan evolution of the Southalpine basement since these data suggest a possible affinity of the Southalpine basement to Gondwana-related tectonic elements as well as to a possible Cadomian hinterland. This study shows that dating detrital zircons of the Brixen Quartzphyllites has great potential for providing age constraints on the complex geological evolution of the Southalpine basement.     

Amphibole and phlogopite in “hybrid” metasomatic bands monitor trace element transfer at the interface between felsic and ultramafic rocks (Eastern Alps,Italy)

Ultramafic rocks in contact to gneisses in the Mt. Hochwart HP mélange (Eastern Italian Alps) preserve a series of metasomatic mineral zones. A phlogopitite with minor tremolite and accessory zircon and apatite forms close to the gneiss (Zone 1). Zone 2 consists of tremolite, phlogopite and anthophyllite followed by Zone 3 with anthophyllite plus minor chlorite and talc. Zone 3 grades into an amphibole–garnet peridotite lens. This reaction zone has been generated by infiltration of hydrous fluids at T of 660–700 °C and P < 1.2 GPa, which occurred during exhumation of coupled continental crust and mantle peridotites.The reaction zone between a trace element-rich (gneiss) and a trace element depleted reservoir (peridotite) allows assessment of local trace element mobility in aqueous fluids. We present the results of in situ LA-ICP-MS trace element analysis of minerals from the reaction zone. Phlogopite is the main host for Large Ion Lithophile Elements (LILE) and contributes significantly to the Li, Ti, Nb, Ta, Pb and Sc budget. Anthophyllite is the main host for Li whereas all other trace elements including Rare Earth Elements (REE) are preferentially incorporated into tremolite. Combined with the abundance of these minerals over the contact zone, the mineral trace element data suggests that the LILE and REE were mobile on a small scale of a few centimetres only. Limited mobility of Ta, which is generally regarded as barely mobile in fluids, is documented in elevated contents of Ta in anthophyllite coupled with low Nb/Ta. The high Li content in minerals throughout the reaction zone suggests that Li was the most mobile element.The studied metasomatic zones mirror geochemical processes occurring in subduction zones at the slab–mantle interface. Phlogopite crystallization at the slab–mantle interface is an efficient mechanism to filter LILE from the aqueous fluid. Thus, such reaction zones, forming at temperatures < 660–700 °C, likely prevents that the typical slab signature with enriched LILE is transported by aqueous fluids over long distances in the mantle wedge. However, if coupled to the downgoing slab, phlogopite- and tremolite-rich rocks from such reaction zones might be able to act as carriers of trace elements and water into deeper parts of the subduction zone.     

Characterization of non-equilibrium and equilibrium occurrences of paragonite/muscovite intergrowths in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy)

 Coexisting muscovite and paragonite have been observed in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy). The P-T conditions of this eclogite reached 570–650 °C and 19–21 kbar and the rocks show several stages of mineral growth during their retrograde path, ranging from the subsequent lower-P eclogite facies to the blueschist facies and then the greenschist facies. Muscovite and paragonite are very common in these rocks and show two texturally different occurrences indicating equilibrium and non-equilibrium states between them. In one mode of occurrence they coexist in equilibrium in the lower-P eclogite facies. In the same rock muscovite ± albite also replaced paragonite during a greenschist-facies overprint, as evidenced by unique across – (001) layer boundaries. The chemical compositions of the lower-P eclogite-facies micas plot astride the muscovite – paragonite solvus, whereas the compositions of the greenschist-facies micas lie outside the solvus and indicate disequilibrium. The TEM observations of the textural relations of the greenschist-facies micas imply structural coherency between paragonite and muscovite along the layers, but there is a sharp discontinuity in the composition of the octahedral and tetrahedral sheets across the phase boundary. We propose that muscovite formed through a dissolution and recrystallization process, since no gradual variations toward the muscovite – paragonite interfaces occur and no intermediate, homogeneous Na-K phase has been observed. Because a solid-state diffusion mechanism is highly unlikely at these low temperatures (300–500 °C), especially with respect to octahedral and tetrahedral sites, it is assumed that H₂O plays an important role in this process. The across-layer boundaries are inferred to be characteristic of such non-equilibrium replacement processes. The characterization of these intergrowths is crucial to avoiding erroneous assumptions regarding composition and therefore about the state of equilibrium between both micas, which in turn may lead to misinterpretations of thermometric results. Received: 3 February 1999 / Accepted: 19 October 1999