Muscovite dehydration melting: Reaction mechanisms,microstructures, and implications for anatexis

Dehydration melting of muscovite in metasedimentary sequences is the initially dominant mechanism of granitic melt generation in orogenic hinterlands. In dry (vapour-absent) crust, muscovite reacts with quartz to produce K-feldspar, sillimanite, and monzogranitic melt. When water vapour is present in excess, sillimanite and melt are the primary products of muscovite breakdown, and any K-feldspar produced is due to melt crystallization. Here we document the reaction mechanisms that control nucleation and growth of K-feldspar, sillimanite, and silicate melt in the metamorphic core of the Himalaya, and outline the microstructural criteria used to distinguish peritectic K-feldspar from K-feldspar grains formed during melt crystallization. We have characterized four stages of microstructural evolution in selected psammitic and pelitic samples from the Langtang and Everest regions: (a) K-feldspar nucleates epitaxially on plagioclase while intergrowths of fibrolitic sillimanite and the remaining hydrous melt components replace muscovite. (b) In quartzofeldspathic domains, K-feldspar replaces plagioclase by K⁺–Na⁺ cation exchange, while melt and intergrowths of sillimanite+quartz form in the aluminous domains. (c) At 7–8 vol.% melt generation, the system evolves from a closed to open system and all phases coarsen by up to two orders of magnitude, resulting in large K-feldspar porphyroblasts. (d) Preferential crystallization of residual melt on K-feldspar porphyroblasts and coarsened quartz forms an augen gneiss texture with a monzogranitic-tonalitic matrix that contains intergrowths of sillimanite+tourmaline+muscovite+apatite. Initial poikiloblasts of peritectic K-feldspar trap fine-grained inclusions of quartz and biotite by replacement growth of matrix plagioclase. During subsequent coarsening, peritectic K-feldspar grains overgrow and trap fabric-aligned biotite, resulting in a core to rim coarsening of inclusion size. These microstructural criteria enable a mass balance of peritectic K-feldspar and sillimanite to constrain the amount of free H₂O present during muscovite dehydration. The resulting modal proportion of K-feldspar in the Himalayan metamorphic core requires vapour-absent conditions during muscovite dehydration melting and leucogranite formation, indicating that the generation of large volumes of granitic melts in orogenic belts is not necessarily contingent on an external source of fluids.     

New constraints on the P–T path of HT/UHT metapelites from the Highland Complex of Sri Lanka

We report here rare evidence for the early prograde P-Tevolution of garnet-sillimanite-graphite gneiss(khondalite)from the central Highland Complex,Sri Lanka.Four types of garnet porphyroblasts(Grt_1,Grt_2,Grt_3 and Grt_4)are observed in the rock with specific types of inclusion features.Only Grt_3 shows evidence for non-coaxial strain.Combining the information shows a sequence of main inclusion phases,from old to young:oriented quartz inclusions at core,staurolite and prismatic sillimanite at mantle,kyanite and kyanite pseudomorph,and biotite at rim in Grt_1;fibrolitic sillimanite pseudomorphing kyanite±corundum,kyanite,and spinel+sillimanite after garnet+corundum in Grt_2;biotite,sillimanite,quartz±spinel in Grt_3;and ilmenite,rulite,quartz and sillimanite in Grt_4.The pre-melting,original rock composition was calculated through stepwise re-integration of melt into the residual,XRF based composition,allowing the early prograde metamorphic evolution to be deduced from petrographical observations and pseudosections.The earliest recognizable stage occurred in the sillimanite field at around 575℃ at 4.5 kbar.Subsequent collision associated with Gondwana amalgamation led to crustal thickening along a P-T trajectory with an average dP/dT of ~30 bar/℃ in the kyanite field,up to ~660℃ at 6.5 kbar,before crossing the wet-solidus at around 675 ℃ at 7.5 kbar.The highest pressure occurred at P 10 kbar and T around 780℃ before prograde decompression associated with further heating.At 825℃ and 10.5 kbar,the rock re-entered into the sillimanite field.The temperature peaked at 900℃ at ca.9-9.5 kbar.Subsequent near-isobaric cooling led to the growth of Grt_4 and rutile at T ~880℃.Local pyrophyllite rims around sillimanite suggest a late stage of rehydration at T400℃,which probably occurred after uplift to upper crustal levels.U-Pb dating of zircons by LAICPMS of the khondalite yielded two concordant ~(206)Pb/~(238)U age groups with mean values of 542±2 Ma(MSWD=0.24,Th/U=0.01-0.03)and 514±3 Ma(MSWD=0.50,Th/U=0.01-0.05)interpreted as peak metamorphism of the khondalite and subsequent melt crystallization during cooling.     

FT-IR Spectroscopic Investigation of Hydrous Components in Sillimanite from Eastern Ghat Granulite Belt, India

FT-IR spectra of sillimanite samples from high grade regionally metamorphosed rocks belonging to the granulite terrain (amphibolite to pyroxene granulite facies) deciphers prominent OH features. Heating experiments indicate growth of prominent band at 3161cm⁻¹. Heating above 1000°C all OH features disappear in intensity into broad features with slight shift of bands towards lower energies. Complete dehydration requires temperatures above 1000°C. Coexistence of boron and OH features are also observed in all sillimanite samples. The high temperature behaviour of sillimanite from the granulite terrain discerns that the hydrous species in sillimanite were incorporated much below 700°C, however, secondary hydration due to pegmatite activity, retrograde metamorphism and migmatisation is not ruled out. Thus a near anhydrous condition were probably not achieved during the granulite facies metamorphism in Eastern ghat granulite terrain.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.     

矽线石成分分析标准物质研制

随着矽线石应用领域的逐步拓展,英国、南非和日本等国家已研制了4种矽线石标准物质,而我国仅有一种矽线石国家二级标准物质,无论从组分的浓度梯度范围还是定值指标等方面,均难以满足我国研究需求。本文针对我国矽线石的分布情况,在黑龙江林口县和河南内乡县采集典型矽线石原矿2种,在黑龙江林口县采集矽线石精矿1种,按照国家一级标准物质研制标准和规范要求,研制了3种矽线石成分分析国家一级标准物质(批准编号为GBW07843、GBW07844、GBW07845)。均匀性检验结果表明,除个别指标(Y-1的TFe_2O_3、Cu和J-1的Mn O等)外,3种标准物质检测指标的F值均小于临界值F0.05(24,25)=1.96,组内和组间无明显差异;Y-1的TFe_2O_3、Cu和J-1的MnO等指标的组内和组间差异主要来源于分析方法误差,由此表明此批标准物质均匀性良好。在14个月考察期内,3种标准物质计算得到的拟合直线斜率b1均不显著,表明3种标准物质有较好的稳定性。经我国10家实验室使用多种分析方法对矿石中的主量元素、痕量元素和矽线石含量(硅铝,SAl_2O_3)等共计39种组分联合定值,各组分的相对扩展不确定度处于0.60%~29.9%区间,3种矽线石标准物质主量成分Al_2O_3的含量分别为25.85%、28.16%和55.06%。该系列矽线石标准物质可满足地质、环境等研究领域相关样品分析质量监控工作的需求。     

Shock-induced formation of kyanite (Al<Subscript>2</Subscript>SiO<Subscript>5</Subscript>) from sillimanite within a dense metamorphic rock from the Ries crater (Germany)

A dense (~3.34 g cm^–3) garnet–sillimanite-rich metamorphic rock from the suevite breccia of the Ries impact crater was studied by scanning-electron microscopy and Raman microprobe spectroscopy. In the strongly shocked rock clast kyanite was formed from sillimanite under momentary high pressures of natural shock waves. Kyanite aggregates were found as thin (~0.3–2.0 m) seams along grain boundaries between, and fractures within, sillimanite grains. Within these seams kyanite c-axes are oriented perpendicular to original grain boundaries and fractures. In addition, larger (up to 10 m) isolated kyanite grains were rarely found within host sillimanite. Filamentary kyanite aggregates and isolated crystals typically show shrinkage cracks due to volume decrease (~10%). Locally, broad interstices between sillimanite crystals are filled with aluminosilicate glass containing a high volume fraction of sub-micrometer-sized euhedral crystals. The silica-rich glass suggests incongruent melting of sillimanite at local post-shock temperatures significantly higher than 1,300°C. The edges of adjacent sillimanite grains are thermally and chemically altered. The local generation of temperature spikes is attributed to strong shock wave interactions due to very high shock impedance contrasts.     

Dislocation strain energy in the Al2SiO5 polymorphs

Molar elastic strain energy arising from dislocations in andalusite and sillimanite were calculated using equations derived from a non-core, linear elasticity model. For perfect (unit) c screw dislocations in these polymorphs, minimum dislocation densities of about 10¹⁰/cm² are necessary to significantly perturb the andalusite=sillimanite equilibrium boundary in P-T space. Compared to unit c dislocations, smaller energy perturbations arise from dissociated c screw dislocations, which are commonly observed in kyanite and sillimanite. A low computed value of stacking fault energy (～30 ergs/cm²) in these polymorphs is compatible with the large separations of dissociated dislocations in these phases. Dislocation densities in naturally occurring Al₂SiO₅ polymorphs are typically <10⁸/cm². Assuming that these densities are representative of those existing during metamorphism, as is supported by the lack of microtextures indicative of strong recovery, it is concluded that molar strain energies corresponding to observed dislocation densities (<10⁸/cm²) result in insignificant perturbation of P-T phase equilibrium boundaries of the Al₂SiO₅ polymorphs.     

Potential protonation sites in the Al<Subscript>2</Subscript>SiO<Subscript>5</Subscript> polymorphs based on polarized FTIR spectroscopy and properties of the electron density distribution

Potential protonation sites for, kyanite, sillimanite, and andalusite, located in a mapping of the (3, −3) critical points displayed by their L(r) = −∇²ρ(r) distributions, are compared with polarized single-crystal FTIR spectra of kyanite and sillimanite determined earlier and with andalusite measured in this study. For andalusite, seven peaks were observed when the electric vector, E, is parallel to [100]: four intense ones at 3,440, 3,460, 3,526, and 3,597 cm⁻¹ and three weaker ones at 3,480, 3,520, and 3,653 cm⁻¹. Six peaks, three intense ones at 3,440, 3,460, and 3,526 cm⁻¹ and three weaker ones at 3,480, 3,520, and 3,653 cm⁻¹ when E parallels [010]. No peaks were observed when E is parallel to [001]. The concentration of water in andalusite varies between 110 and 168 ppm by weight % H₂O. Polarized FTIR spectra indicate that the OH vector is parallel to (001) in andalusite and sillimanite and in kyanite. Examination of the L(r) (3, −3) critical points in comparison with the polarized FTIR indicates that H prefers to bond to the oxygen atoms O1 and O2 in andalusite and O2 and O4 in sillimanite which correspond to the underbonded oxygen atoms and those with the largest L(r) maxima. In kyanite, comparison of the FTIR spectrum and the critical points indicates that H will preferentially bond to the two 4-coordinated O2 and O6 atoms.     

Evidence for cyclic reactions between andalusite, “sericite” and sillimanite, mount franks area, willyama complex N.S.W

In the Mt. Franks area of the Willyama Complex, microfabric evidence suggests that the alteration of andalusite to sillimanite has taken place by a process similar to that suggested by Carmichael (1969). Andalusite is pre- to syn-S₂ in age. Alteration to “sericite” has resulted in the formation of “sericite” laths, some of which are crenulated about S₂, and some which are syn- and post-S₂. “Fibrolite” occurs in these andalusite—“sericite” aggregates within the sillimanite zone and is wholly embedded in “sericite”. “Fibrolite” is pre- to syn-S₂ in age. This evidence is interpreted as suggesting that the formation of sillimanite from andalusite took place via a “sericite” phase.Further microfabric observations are interpreted to imply constant volume for the reaction aluminosilicate → “sericite”. This suggests a situation in which Al³⁺ is relatively mobile but Al⁴⁺ is relatively immobile. This suggestion differs from Carmichael's (1969) idea of Al³⁺ immobility.     

The application of ionic equilibria to metamorphic differentiation: An example

Mineral segregations formed by metamorphic differentiation are an important source of information on diffusion processes in metamorphism. Segregations consisting of andalusite-biotite-quartz cores surrounded by a quartz-feldspar mantle in sillimanite-biotitefeldspar-quartz gneiss near Västervik, Sweden (Loberg, 1963) formed by core-to-mantle migration of K, and mantle-to-core migration of Fe, Mg and Ca. These migrations can be represented by a set of interconnected ionic equilibria involving reaction of microcline and Fe(OH)⁺ in the core to form andalusite plus biotite, and reaction of K⁺, sillimanite and biotite in the mantle to form microcline. Equilibrium constants for these reactions, calculated for conditions inferred from the mineral assemblage and biotite composition, indicate gradients of K⁺ activity (higher in core) and Fe(OH)⁺ activity (higher in mantle). These gradients result simply from the free energy difference between andalusite and sillimanite, without invoking pre-existing megascopic inhomogeneities in the rock or surface energy effects. Although small, these gradients appear to be capable of driving the segregation process.     

Compositional restraints on the sillimanite paragenesis in metapelites from Kuanthal,district Udaipur,India

The rocks exposed in the area around Kuanthal represent one of the oldest Precambrian formations of India and constitute the Banded Gneissic Complex (B.G.C.) of Heron (1953). The main rock types are staurolite-sillimanite schists/gneisses, sillimanite gneisses with or without K-feldspar, migmatites and amphibolites, often intimately and inextricably mixed up with one another. The petrochemical studies of the metapelitic rocks show that the formation of sillimanite is controlled by parent rock chemistry. The critical controlling parameters area: alumina, alkalies (Na₂O + K₂O) and oxidation ratio of rocks. These criteria are equally valid for other well-known areas of high-grade metamorphism. The validity of this proposition has been tested by statistical methods such as multivariate analysis and Mahalonbis's generalized distance D². The linear discriminant function controlling sillimanite paragenesis in metapelites has been worked out and an equation has been evolved to delineate the ‘SB’ (sillimanite-bearing) and ‘SF’ (sillimanite-free) rocks.     

Petrogenesis of andalusite–kyanite–sillimanite veins and host rocks, Sanandaj-Sirjan metamorphic belt, Hamadan, Iran

Quartz‐rich veins in metapelitic schists of the Sanandaj‐Sirjan belt, Hamadan region, Iran, commonly contain two Al₂SiO₅ polymorphs, and, more rarely, three coexisting Al₂SiO₅ polymorphs. In most andalusite and sillimanite schists, the types of polymorphs in veins correlate with Al₂SiO₅ polymorph(s) in the host rocks, although vein polymorphs are texturally and compositionally distinct from those in adjacent host rocks; e.g. vein andalusite is enriched in Fe₂O₃ relative to host rock andalusite. Low‐grade rocks contain andalusite + quartz veins, medium‐grade rocks contain andalusite + sillimanite + quartz ± plagioclase veins, and high‐grade rocks contain sillimanite + quartz + plagioclase veins/leucosomes. Although most andalusite and sillimanite‐bearing veins occur in host rocks that also contain Al₂SiO₅, kyanite‐quartz veins crosscut rocks that lack Al₂SiO₅ (e.g. staurolite schist, granite). A quartz vein containing andalusite + kyanite + sillimanite + staurolite + muscovite occurs in andalusite–sillimanite host rocks. Textural relationships in this vein indicate the crystallization sequence andalusite to kyanite to sillimanite. This crystallization sequence conflicts with the observation that kyanite‐quartz veins post‐date andalusite–sillimanite veins and at least one intrusive phase of a granite that produced a low‐pressure–high‐temperature contact aureole; these relationships imply a sequence of andalusite to sillimanite to kyanite. Varying crystallization sequences for rocks in a largely coherent metamorphic belt can be explained by P–T paths of different rocks passing near (slightly above, slightly below) the Al₂SiO₅ triple point, and by overprinting of multiple metamorphic events in a terrane that evolved from a continental arc to a collisional orogen.     

Order disorder in sillimanite

AP³⁺-Si⁴⁺ disordering in sillimanite cannot be considered as ideal mixing on tetrahedral sites. Ideal free energy of mixing in sillimanite corresponding to slight disordering results in changing the kyanite-sillimanite phase equilibrium boundary by impossible magnitude. A regular solution model for the sites yields the following expression for the free energy of mixing: 1 $$G_{sill}^M = W \{ (X_{Al - T1} )^2 + (X_{Al - T2} )^2 \} + RT ln X_{Al - T1} X_{Al - T2}$$ . Calculations using the phase equilibrium data show that even small disequilibrium in intra-crystalline distribution results in significant change in pressure of the kyanite-sillimanite “equilibrium”. If information on interaction energies such as W is not available for disordering silicates, it is not advisable to use the ideal configurational entropy in calculations of phase equilibria.     

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: II. Andalusite and sillimanite

This paper is an extension of the earlier one dealing with kyanite in which the best fitting value of the oxygen ligand distance for Cr³⁺ is adopted to study the spectroscopic properties of Cr³⁺ ions doped at the two possible Al sites in the other two polymorphs of the aluminosilicate group (Al₂O₃ · SiO₂), namely, andalusite and sillimanite. The superposition model and the crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals are used to predict energy levels and statevectors within the whole 3d ³ configuration. Then the values of the ground state zerofield splitting for Cr³⁺ ions at each Al sites in the two crystals are obtained. The splittings of the lower excited states ² E and ⁴ T ₂ as well as the admixture of ⁴ T ₂ into ² E have also been predicted. Comparison of our results with the available experimental data enable us to correlate the optical and EPR Spectroscopic properties with the substitutional Cr³⁺ sites. The conclusion is that in andalusite and sillimanite only the Al sites with nearly-octahedral six-fold coordination seem to be occupied by Cr³⁺ ions.     

夕线石成因讨论

本文通过夕线石的结构、成分及产出状态,系统讨论和总结了其变质形成过程.含夕线石的变质岩原岩未必对应泥质岩,富夕线石岩石成分上更不能与任何的泥质岩成分对应.原岩本身富铝如多数泥质岩是形成夕线石非常有利的成分条件,但是,即使有合适的温压条件,也未必能够形成夕线石,组分的差异性迁移才是夕线石形成的必要条件.夕线石的形成与变形...     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.     

Cordierite gneisses of southern Kerala,India: petrology,fluid inclusions and implications for crustal uplift history

The cordierite-bearing gneisses occurring as elongate patches in an 8- to 10-km-wide zone along the Achankovil fault-lineament at the northern margin of the southern Kerala crustal segment represent an important lithological unit in the Archaean granulite terrane of south India. The textural relationships in these rocks are consistent with the following main reactions: (1) garnet+quartz=cordierite+hypersthene; (2) garnet+sillimanite+quartz=cordierite; (3) hypersthene+sillimanite+quartz=cordierite; (4) sillimanite+spinel=cordierite+corundum; and (5) biotite+quartz+sillimanite=cordierite+K-feldspar. Many of the mineral associations and reaction textures, including the remarkable preservation of symplectites, are indicative of partial replacement of high-pressure assemblages by cordierite-bearing lower-pressure ones during an event of rapid decompression. Temperature estimates from coexisting mineral phases show 710° (garnet-biotite), 791° (garnet-cordierite) and 788° C (garnet-orthopyroxene). Pressure estimates from mineral assemblages range from 5.4 to 7 kb. Detailed fluid inclusion studies in quartz associated with cordierite show high-density CO₂ (0.80–0.95 g/cm³) as the dominant fluid phase, with traces of probable CH₄ (?) in the sillimanite-bearing rocks. The isochore for the higher-density fluid inclusions defines a pressure of 5.5 kb. The fracture-bound CO₂ and CO₂-H₂O (±CH₄?) inclusions indicate simultaneous entrapment at 400° C and 1.7 kb in the cordierite-hypersthene assemblage and 340° C and 1.2 kb in the cordierite-sillimanite assemblage. The P-T path delineated from combined solid and fluid data corresponds to the piezothermic array of the gneisses and is characterized by T-convex nature, indicative of rapid and virtually isothermal crustal uplift, probably aided by extensional tectonics.     

Oxygen isotope geochemistry of the Omeo Metamorphic Complex,Victoria: Implications for metamorphic fluid flow,mineralisation and anatexis

Metamorphosed turbidites from the Omeo Metamorphic Complex show only minor changes in δ¹⁸O values with increasing metamorphic grade from 13.4 ± 1.7% in the chlorite and biotite zones to 12.3 ± 1.0% in the sillimanite + K‐feldspar zone. Rocks within 5 km of the S‐type granite at Hume Dam have δ¹⁸O values of 6.8–8.1% that probably reflect interaction with heated meteoric‐igneous fluids. Interaction with igneous fluids has also occurred close to other I‐ and S‐type granites in this region. However, pervasive metamorphic fluid‐rock interaction in this terrain did not occur, which limits the region's potential for hydrothermal mineralisation. Anatexis at high grades was probably via dehydration‐melting reactions that consumed muscovite and biotite, which is consistent with there being little fluid present during metamorphism. Small (kilometre scale or less) S‐type granites in the sillimanite + K‐feldspar zone have δ¹⁸O values similar to those of the surrounding metasediments and probably formed by melting of those rocks. By contrast, larger (tens of kilometres scale) Ca‐rich, peraluminous, S‐type granites have lower δ¹⁸O values than the surrounding metasediments, and may represent melts of underlying middle to lower crust.     

Variations in the transient prograde geothermal gradient from chloritoid-staurolite equilibria: a case study from the Barrovian and Buchan-type domains in the Bohemian Massif

Thermodynamic modelling of metamorphic rocks increases the possibilities of deciphering prograde paths that provide important insights into early orogenic evolution. It is shown that the chloritoid–staurolite transition is not only an indicator of temperature on prograde P–T paths, but also a useful indicator of pressure. The approach is applied to the Moravo‐Silesian eastern external belt of the Bohemian Massif, where metamorphic zones range from biotite to staurolite‐sillimanite. In the staurolite zone, inclusions of chloritoid occur in garnet cores, while staurolite is included at garnet rims and is widespread in the matrix. Chloritoid X_Fe = 0.91 indicates transition to staurolite at 5 kbar and 550 °C and consequently, an early transient prograde geothermal gradient of 29 °C km^?1. The overall elevated thermal evolution is then reflected in the prograde transition of staurolite to sillimanite and in the achievement of peak temperature of 660 °C at a relatively low pressure of 6.5 kbar. To the south and to the west of the studied area, high‐grade metamorphic zones record a prograde path evolution from staurolite to kyanite and development of sillimanite on decompression. Transition of chloritoid to staurolite was reported in two places, with chloritoid X_Fe = 0.75–0.80, occurring at 8–10 kbar and 560–580 °C, and indicating a transient prograde geothermal gradient of 16–18 °C km^?1. These data show variable barric evolutions along strike and across the Moravo‐Silesian domain. Elevated prograde geothermal gradient coincides with areas of Devonian sedimentation and volcanism, and syn‐ to late Carboniferous intrusions. Therefore, we interpret it as a result of heat inherited from Devonian rifting, further fuelled by syntectonic Carboniferous intrusions.     

Biotite and garnet compositional variation and mineral equilibria in Grenville gneisses of the Otter Lake area, Quebec

Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe²⁺/(Fe²⁺+ Fe³⁺) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe²⁺ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe³⁺, Ti, and Al, and some are vacant. Mg/(Mg + Fe²⁺), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H₂O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H₂O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe²⁺ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln K_D= 1.3 + 2.5 × 10^?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe²⁺+ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.