Dehydration melting of micas in the Chilka Lake Khondalites: The link between the metapelites and granitoids

Garnet-sillimanite gneisses, locally known as khondalites, occur abundantly in the Chilka Lake granulite terrane belonging to the Eastern Ghats Proterozoic belt of India. Though their chemistry has been modified by partial melting, it is evident that the majority of these rocks are metapelitic, with some tending to be metapsammitic. Five petrographically distinct groups are present within the khondalites of which the most abundant group is characteristically low in Mg:Fe ratios — the main chemical discriminant separating the five groups. The variations in Mg:Fe ratios of the garnets, biotites, cordierites, orthopyroxenes and spinels from the metapelites are compatible with those in the bulk rocks. A suite of granitoids containing garnet, K-feldspar, plagioclase and quartz, commonly referred to as leptynites in Indian granulite terranes, are interlayered with khondalites on the scale of exposures; in a few spots, the intercalated layers are thin. The peraluminous character of the leptynites and presence of sillimanite trails within garnets in some of them suggest derivation of leptynites by partial melting of khondalites. Here we examine this connection in the light of results derived from dehydration melting experiments of micas in pelitic and psammitic rocks. The plots of leptynites of different chemical compositions in a (MgO + FeO)-Na₂O-K₂O projection match the composition of liquids derived by biotite and muscovite dehydration melting, when corrected for co-products of melting reactions constrained by mass balance and modal considerations. The melt components of the leptynites describe four clusters in the M-N-K diagram. One of them matches melts produced dominantly by muscovite dehydration melting, while three clusters correspond to melting of biotite. The relative disposition of the clusters suggests two trends, which can be correlated with different paths that pelitic and psammitic protoliths are expected to generate during dehydration melting. Thus the leptynites evidently represent granitoids which were produced by dehydration melting in metapelites of different compositions. The contents of Ti, Y, Nb, Zr and Th in several leptynites indicate departures from equilibrium melt compositions, and entrainment of restites is considered to be the main causative factor. Disequilibrium in terms of major elements is illustrated by leucosomes within migmatites developed in a group of metapelites. But the discrete leptynites that have been compared with experimental melts approach equilibrium melt compositions closely.     

Positron annihilation lifetime spectral changes on dehydration of natural beryls and cordierites

The effect on positron annihilation lifetime spectra, measured at room temperature, of the dehydration of single crystals of beryl and cordierite was studied. In each case, the spectra were satisfactorily fitted to three lifetime components. For the beryls, the dehydration considerably enhanced the intensity of the intermediate-lifetime component (I ₂) and reduced the intensity of the longest-lived component (I ₃). I ₂ is attributed to positron annihilation in the empty cages in the channels of the beryl structure and I ₃ to annihilation by a pick-off process via unknown foreign molecules. However, for the cordierites, the main effect of the dehydration was a slight (～10%) increase in the lifetime of the intermediate component, τ₂. Here I ₂ was relatively high both before and after dehydration and the increase in τ₂ is attributed to Si-Al ordering. No changes in the lifetime spectra were produced by γ irradiation.     

Cordierite III: the site occupation and concentration of Fe3+

Cordierite has the ideal formula (Mg,Fe)₂Al₄Si₅O₁₈ ^.x(H₂O,CO₂), but it must contain some Fe³⁺ to account for its blue color and strong pleochroism. The site occupation and concentration of Fe³⁺ in two Mg-rich natural cordierites have been investigated by EPR and ⁵⁷Fe Mössbauer spectroscopy. In addition, powder IR spectroscopy, X-ray diffraction, and TEM examination were used to characterize the samples. Single-crystal and powder EPR spectra indicate that Fe³⁺ is located on T₁1 in natural cordierites and not in the channels. The amount in Mg-rich cordierites is very small with an upper limit set by Mössbauer spectroscopy giving less than 0.004 cations per formula unit (pfu). Fe³⁺ in cordierite can, therefore, be considered insignificant for most petrologic calculations. Heat-treating cordierite in air at 1,000?°C for 2?days causes an oxidation and/or loss of Fe²⁺ on T₁1, together with an expulsion of Na⁺ from the channels, whereas heating at the Fe–FeO buffer produces little Fe³⁺ in cordierite. Heating at 1,000?°C removes all class I H₂O, but small amounts of class II H₂O remain as shown by the IR measurements. No evidence for channel Fe²⁺ or Fe³⁺ in the heat-treated samples was found. The blue color in cordierite arises from a broad absorption band (E//b and weaker with E//a) around 18,000?cm^?1 originating from charge-transfer between Fe²⁺ in the octahedron and Fe³⁺ in the edge-shared T₁1 tetrahedron. It therefore appears that all natural cordierites contain some tetrahedral Fe³⁺. The brown color of samples heated in air may be due to the formation of very small amounts of submicroscopic magnetite and possibly hematite. These inclusions in cordierite can only be identified through TEM study.     

Structural chemistry of synthetic cordierite: Evidence for solid solutions and disordered compositional domains in Bi-flux-grown Mg-cordierites

The structure, crystal chemistry, and microstructure of disordered and ordered Mg-cordierites synthesized in a bismuth oxide flux system have been studied by a combination of x-ray and neutron powder diffraction and quantitative x-ray microanalysis using analytical electron microscopy. Microchemical data obtained on Bi-flux cordierites using energy-dispersive x-ray analysis is interpreted through comparison with data collected on stoichiometric Mg₂Al₄Si₅O₁₈ glass and α- and β-cordierite samples synthesized by subsolidus crystallization of the glass. Bi-flux cordierites crystallize in both the hexagonal and orthorhombic polymorphs and contain 5 to 10 at% occupancy of bismuth on the C1 and C2 channel sites. The microstructure of Bi-flux α-cordierite is characterized by the existence of local domains of disordered cordierite solid solutions with variable composition and significant vacancy concentrations on the octahedral site. The β-cordierites have a more homogeneous microstructure but are still Al-deficient, Si-rich solid solutions.     

Fe-rich cordierites from acid volcanic rocks,an optical and x-ray single-crystal structure study

Low-cordierites from volcanic rocks of Tuscany (Italy), Lipari (Italy), and of the Cerberean Cauldron (Australia) were investigated. Both single crystal structure refinements and optical data indicate that the Italian samples contain only low concentrations of volatiles (<0.3 wt.%), whereas in the crystals from the Cerberean Cauldron more than 50% of the structural channels are occupied, preferentially by H₂O (1.6–1.9 wt.%). This high volatile concentration is in qualitative agreement with the estimated p,T-conditions (4–4.5 kbar at 750–780° C) of the magma prior to eruption. In contrast, the Italian cordierites have formed at temperatures above 950° C and pressures below 2 kbars. Low-cordierites of volcanic origin reveal the same high degree of Si, Al-ordering as observed for low-cordierites from metamorphic rocks and pegmatites. The crystals studied possess F(mol)=(Fe+Mn)/(Fe+Mn+Mg)>0.4 and provide additional information about the crystal structure of Fe-rich cordierites. With increasing FeMg substitution the mean T₁1(Al)-O distance decreases slightly, which is probably not caused by substitution of smaller cations on t₁1 but by angular distortion of the tetrahedron.     

Potassic cordierites: characteristic minerals for high-temperature,very low-pressure environments

The mineral chemistry of cordierites from three different sanidinite facies localities-1) volcanic xenoliths from the Eifel, Germany; 1) buchites of the Blaue Kuppe, Germany; 3) paralavas from the Bokaro coalfield, India-is characterized by unusually high potassium contents up to 1.71 wt%, equivalent to 0.22 K atoms per formula unit (p.f.u.) based on 18 oxygens. Significantly, these cordierites are either hexagonal highcordierites (indialites) with =0 or exhibit intermediate -values 0<<0.20 relative to well Al,Si-ordered orthorhombic low-cordierite. Based on microprobe analyses, the predominant substitutional mechanism for alkali incorporation is Alk^[Channel]+Al^[4] for +Si^[4], thus leading to Al/Si-ratios deviating considerably from the value 4:5 in ideal cordierite M₂[Al₄Si₅O₁₈]. The most highly substituted cordierite from Blaue Kuppe is about (K_0.22Na_0.07)^[Ch](Mg_1.33Fe _0.66 ²⁺ )^[6][Al_4.16Si_4.79O₁₈]. Bokaro cordierites are further characterized by obvious (Al+Si)-deficiencies against the ideal value of 9.0 p.f.u., a tendency of which is apparent in most Blaue Kuppe analyses as well. As the tetrahedral deficiencies are often equivalent to excess cations in the octahedra, we assume that ferric iron fills up the remaining tetrahedral sites, again linked with the introduction of potassium according to K+Fe³⁺ for +Si. In comparison with the available experimental data, these natural potassic cordierites are considered stable high-temperature phases regarding their compositions, but not their structural states. Although the substitution KAl for Si in Mg-cordierite is known to lower the maximum -value to be attained, the hexagonal nature of the cordierites must be due to very rapid crystallization and subsequent quenching. The higher -values of the Blaue Kuppe cordierites might be caused by their topotactic origin from preexisting biotite. The complicated twin and domain patterns of the hexagonal Eifel and Bokaro cordierites as observed in thin section could perhaps be attributed to structural modulations as postulated recently for hexagonal cordierite shortly after its growth.     

A new sodian-beryllian cordierite from Soto,Argentina, and the relationship between distortion index,Be content,and state of hydration

In a cordieritite marking the contact of a granite massif one of the large porphyroblasts of cordierite was found to contain relatively high amounts of BeO (0.93 wt.%) and Na₂O (1.25 wt.%), while others are very poor in these components. Na and Be were introduced following the substitution NaBeAl. Like in other sodian beryllian cordierites the distortion index is low (0.12), and a negative correlation between and Be contents is established using additional data from the literature.Dehydration of NaBe-cordierites through heating consistently leads to increasing , and subsequent hydrothermal rehydration of the Soto sample reestablished low . This behavior is consistent with that implied by the model of Stout (1975) which, however, does not apply to the pure system Mg-cordierite-water. Nevertheless it is not certain that the unusual behavior of NaBe-cordierites is due to hydrogen bonding of H₂O molecules within the structural channels of cordierite to oxygens of the framework, although the Type II water molecules occurring exclusively in alkali-bearing cordierites and having their H-H vectors parallel [010] (Goldman et al. 1977) would seem mechanically fitter to have this effect than the Type I water with H-H parallel [001] as proposed by Stout (1975). An alternative explanation of this dehydration/rehydration behavior implies positional shifts of sodium within the channels depending on whether or not water is available.     

Optical methods of determination of the water contents in cordierites

Equations of linear regression were derived for the determination of water contained in cordierites. The accuracy of measurements of refraction indices being ±0.001, the accuracy of quantitative evaluation of H₂O was ±0.13 wt %.     

Enthalpy effects associated with Al/Si ordering in anhydrous Mg-cordierite

Measurements of the heats of solution (ΔH_soln) in molten Pb₂B₂O₅ at 708°C of anhydrous magnesian cordierites, prepared with a range of structural states, show that the enthalpy effect associated with Al/Si ordering is substantial (? 9.76 ± 1.56 kcal mole^?1). Differences in the state of order between synthetic cordierites used in phase equilibrium studies and cordierites in the natural environment could lead to significant errors in the estimation of palaeo-pressures and temperatures. A continuous change of ΔH_soln with annealing time supports the suggestion of putnis (1980) that the hexagonal → orthorhombic transformation in cordierite, which can occur via a modulated structure, is truly continuous under metastable conditions. In addition, a linear relation between ΔH_soln and the logarithm of annealing time has been found, which provides some insight into the nature of the ordering mechanisms at an atomic level. Al and Si exchanges occur continuously between neighbouring tetrahedral sites with a net drift towards increasing order. No kinetic or thermochemical distinction can be made between the development of long range and short range order.The enthalpy of vitrification (~ 12 kcal mole^?1) for a metastable stuffed β-quartz polymorph of cordierite composition is similar to that for pure quartz (on a per two oxygen basis), while the heat of vitrification for even the most disordered cordierite seen in this study is more than a factor of three greater (~40 kcal mole^?1). This is consistent with the view that cordierite glass resembles the quartz structure more closely than the crystalline cordierite structure, and that crystallisation of the glass below ~900°C is controlled by a tetrahedral framework.     

Experimental study of metamorphic reactions and dehydration processes at the blueschist–eclogite transition during warm subduction

The transition between blueschist and eclogite plays an important role in subduction zones via dehydration and densification processes in descending oceanic slabs. There are a number of previous petrological studies describing potential mineral reactions taking place at the transition. An experimental determination of such reactions could help constrain the pressure–temperature conditions of the transition as well as the processes of dehydration. However, previous experimental contributions have focused on the stability of spontaneously formed hydrous minerals in basaltic compositions rather than on reactions among already formed blueschist facies minerals. Therefore, this study conducted three groups of experiments to explore the metamorphic reactions among blueschist facies minerals at conditions corresponding to warm subduction, where faster reaction rates are possible on the time scale of laboratory experiments. The first group of experiments was to establish experimental reversals of the reaction glaucophane+paragonite to jadeite+pyrope+quartz+H₂O over the range of 2.2–3.5 GPa and 650–820°C. This reaction has long been treated as key to the blueschist–eclogite transition. However, only the growth of glaucophane+paragonite was observed at the intersectional stability field of both paragonite and jadeite+quartz, confirming thermodynamic calculations that the reaction is not stable in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O. The second set of experiments involved unreversed experiments using glaucophane+zoisite ±quartz in low‐Fe and Ca‐rich systems and were run at 1.8–2.4 GPa and 600–780°C. These produced omphacite+paragonite/kyanite+H₂O accompanied by compositional shifts in the sodium amphibole, glaucophane, towards sodium–calcium amphiboles such as winchite (?(CaNa)(Mg₄Al)Si₈O₂₂(OH)₂) and barroisite (?(CaNa)(Mg₃Al₂)(AlSi₇)O₂₂(OH)₂). This suggests that a two‐step dehydration occurs, first involving the breakdown of glaucophane+zoisite towards a paragonite‐bearing assemblage, then the breakdown of paragonite to release H₂O. It also indicates that sodium–calcium amphibole can coexist with eclogite phases, thereby extending the thermal stability of amphibole to greater subduction zone depths. The third set of experiments was an experimental investigation at 2.0–2.4 GPa and 630–850°C involving a high‐Fe (Fe#=Fe_total/(Fe_total+Mg)≈0.36) natural glaucophane, synthetic paragonite and their eclogite‐forming reaction products. The results indicated that garnet and omphacite grew over most of these pressure–temperature conditions, which demonstrates the importance of Fe‐rich glaucophane in forming the key eclogite assemblage of garnet+omphacite, even under warm subduction zone conditions. Based on the experiments of this study, reaction between glaucophane+zoisite is instrumental in controlling dehydration processes at the blueschist–eclogite transition during warm subduction.     

Heating and radiation effects on optical and mössbauer spectra of Fe-bearing cordierites

Optical spectroscopy indicated that the partial oxidation of Fe²⁺ to Fe³⁺ on heating natural cordierites above ～500° C was not sensitive to oxygen partial pressure. This result suggested that the partial oxidation takes place by loss of mobile charge compensators such as protons. Ionizing radiation also produced partial oxidation of the minor-site Fe²⁺ to Fe³⁺, but this effect could be reversed by annealing at ～300° C and so was due only to an electronic redistribution. Mössbauer spectroscopy confirmed these results, although there were complications due to apparent thermal decomposition in localized regions of the cordierites on heating in air. Ionizing radiation also produced strong absorption in the near-ultraviolet and blue regions of the optical spectrum. This absorption, which was strongest in the α polarization, had different annealing characteristics to those of the crystal-field absorption bands near 10,000 cm^?1. Dehydration by heating above ～900° C severely reduced the subsequent effect of ionizing radiation on the optical spectra. On heating over a temperature range spanning the dehydration temperature, the lack of any changes in the absorption energies of the β- and γ-polarized crystal field bands near 10,000 cm^?1, of any changes in the ratio of the intensities of these β- and γ-polarized crystal field bands, and of any singularity in the intensity variations of the bands with heating temperature, all suggest that these bands originate from substitutional Fe²⁺ rather than Fe²⁺ in channel sites. Mössbauer evidence also supports this. The formation of pleochroic haloes in cordierite is discussed briefly. No evidence of CO _- ³ centres in the irradiated samples was found.     

Garnet-cordierite gneisses near the Egersund-Ogna anorthositic intrusion, southwestern Norway

Graphite-bearing garnet-cordierite rocks from the Sjelset-Vikesá region, south Bogaland, Norway have been analysed by microprobe methods. The garnets belong to the pyropealmandine series and contain 28 mole% pyrope, while the cordierites contain about 71% of the Mg end-member. A regional temperature of about 720–750°C and a lithostatic pressure in the order of 6–7 kb have been inferred from the garnet and cordierite compositions. The petrographic observation suggests that such P---T conditions might reflect a retrograde metamorphic event. A tentative estimation of the fluid phase composition, based on the study of opaque minerals, is presented.     

Deformation and recrystallisation mechanisms in naturally deformed cordierite

Cordierite — (Mg,Fe)₂Al₄Si₅O₁₈ — occurs as porphyroclasts within metapelitic and metavolcanic rocks from the Kemiö-Orijärvi belt, SW Finland. After crystallisation the cordierites have been deformed at temperatures between 550–825° C and pressures of 3–5 kbar. Optical microscopy reveals the following deformation-induced microstructures: a bimodal size distribution between host, 0.3 to 4.0 mm, and recrystallised (new) grains, 0.1 to 0.5 mm; the intracrystalline defect-structures of host grains yield undulatory extinction, subgrains and some twinning. Recrystallised grains are optically strain free. Grain and subgrain boundaries are generally straight and parallel to crystallographic low-index planes. Orientation distribution diagrams for host and recrystallised grains yield similar fabric diagrams, i.e. [010] perpendicular to foliation -S-, [001] and [100] parallel to S and [001] parallel to lineation -L-. The fabric diagrams indicate that [001] (010) is the dominant slip system. Transmission electron microscopy reveals straight free dislocations, glide and climb loops, minor {130} and {110} microtwins, isolated nodal points and dislocation walls. Contrast analyses yield Burgers vector b = [001] being dominant and b = [100] subordinate. Climb loops consist of 〈c〉-dislocations that are dissociated in (001) planes, glide loops are defined by [100] [010] and [001] (100). The cordierite microstructures have been interpreted to be generated by dislocation creep. The dominant recrystallisation mechanism is thought to be subgrain rotation subsequently followed by minor grain or twin-band boundary migration.     

Dehydration melting of tonalites. Part I. Beginning of melting

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996     

Experimental Study of the Melting Reaction and Genetic Mechanism of Mineral Phase Transformation in Granulite Facies Metamorphism

The high-temperature and high-pressure experiment on natural block rock indicates that dehydration-melting of hydrous biotite (Bi) and partial melting of felsic minerals in garnet-biotite-plagioclase gneiss are mainly controlled by temperature, while mineral phase transformation is not only controlled by temperature-pressure conditions but also genetically associated with hydrous mineral dehydration-melting and partial melting of felsic minerals. According to the characteristics of biotite dehydration-melting and garnet transformation reaction, three stages may be distinguished: (1) when the experimental temperature is 700℃, biotite transforms to ilmenite (Ilm) + magnetite (Mt) + H2O and garnet to magnetite (Mt); (2) when the temperature is 730-760℃, biotite is dehydrated and melted and transformed into K2O-rich melt + Ilm + Mt, and garnet, into hypersthene (Hy) + cordierite (Crd); (3) when the temperature is up to or higher than 790℃, biotite is dehydrated and melted and transformed into melt + Hy +     

An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K2O–Na2O–CaO–MgO–MnO–FeO–Fe2O3–Al2O3–TiO2–SiO2–C–H2–O2

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–X_CO2–f_O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H₂O and CO₂ contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.     

Rare earth element–SiO<Subscript>2</Subscript> systematics of island arc crustal amphibolite migmatites from the Asago body of the Yakuno Ophiolite,Japan: a field evaluation of some model predictions

The two most commonly invoked processes for generating silicic magmas in intra-oceanic arc environments are extended fractional crystallization of hydrous island arc basalt magma or dehydration melting of lower crustal amphibolite. Brophy (Contrib Mineral Petrol 156:337–357, 2008) has proposed on theoretical grounds that, for liquids >~65 wt% SiO₂, dehydration melting should yield, among other features, a negative correlation between rare earth element (REE) abundances and increasing SiO₂, while fractional crystallization should yield a positive correlation. If correct, the REE–SiO₂ systematics of natural systems might be used to distinguish between the two processes. The Permian-age Asago body within the Yakuno Ophiolite, Japan, has amphibolite migmatites that contain felsic veins that are believed to have formed from dehydration melting, thus forming an appropriate location for field verification of the proposed REE–SiO₂ systematics for such a process. In addition to a negative correlation between liquid SiO₂ and REE abundance for liquids in excess of ~65 % SiO₂, another important model feature is that, at very high SiO₂ contents (75–76 %), all of the REE should have abundances less than that of the host rock. Assuming an initial source amphibolite that is slightly LREE-enriched relative to the host amphibolites, the observed REE abundances in the felsic veins fully support all theoretical predictions.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores. X. thermal stability and dehydration features of synthetic analogs of the cobaltomenite–ahlfeldite solid solution series

The aim of this study is the experimental investigation of the synthetic analogs of cobaltomenite, CoSeO₃ ? 2H₂O, ahlfeldite, NiSeO₃ ? 2H₂O, members of the cobaltomenite–ahlfeldite solid solution series (Ni _x Co_1–x )SeO₃ ? 2H₂O, and singularities of their dehydration and dissociation. The intermediate members of the cobaltomenite (CoSeO₃ ? 2H₂O)–ahlfeldite (NiSeO₃ ? 2H₂O) series have been synthesized and studied with a combination of X-ray diffraction, scanning electron microscopy, and the simultaneous application of thermogravimetry (TG) and differential scanning calorimetry (DSC) within the temperature range from 25 to 640°C. The complete solid solution series corresponds to the monoclinic space group P2₁/n. Unit-cell dimensions decrease in all crystallographic directions as the amount of Ni increases. The angle β increases from 98.82(1) (cobaltomenite) to 99.05(1)° (ahlfeldite). It has been established that CoSeO₃ ? 2H₂O and NiSeO₃ ? 2H₂O dehydrate at 120–340°C through two stages apparently corresponding, to the formation of intermediate hydrated species CoSeO₃ ? H₂O and NiSeO₃ ? 1/3H₂O. The reaction enthalpies for each dehydration stage of CoSeO₃ ? 2H₂O and NiSeO₃ ? 2H₂O have been determined. Changes of the unit-cell dimensions and dehydration temperatures are rationalized in terms of the Co and Ni site occupancy in the structure of the cobaltomenite–ahlfeldite solid-solution series members.     

Experimental and petrological constraints on local-scale interaction of biotite-amphibole gneiss with H2O-CO2-（K, Na）Cl fluids at middle-crustal conditions： Example from the Limpopo Complex, South Africa

Reaction textures and fluid inclusions in the～2.0 Ga pyroxene-bearing dehydration zones within the Sand River biotite-hornblende orthogneisses（Central Zone of the Limpopo Complex） suggest that the formation of these zones is a result of close interplay between dehydration process along ductile shear zones triggered by H₂O-CO₂-salt fluids at 750—800℃and 5.5—6.2 kbar.partial melting,and later exsolution of residual brine and H₂O-CO₂ fluids during melt crystallization at 650—700℃.These processes caused local variations of water and alkali activity in the fluids,resulting in various mineral assemblages within the dehydration zone.The petrological observations are substantiated by experiments on the interaction of the Sand River gneiss with the H₂O-CO-2-（K,Na）Cl fluids at 750 and 800℃and 5.5 kbar.It follows that the interaction of biotite-amphibole gneiss with H₂O-CO₂-（K.Na）Cl fluids is accompanied by partial melting at 750—800℃.Orthopyroxene-bearing assemblages are characteristic for temperature 800℃and are stable in equilibrium with fluids with low salt concentrations,while salt-rich fluids produce clinopyroxene-bearing assemblages.These observations arc in good agreement with the petrological data on the dehydration zones within the Sand River orthoeneisses.     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.