Water molecules in beryl and cordierite: high-temperature vibrational behavior,dehydration, and coordination to cations

Natural samples of typical cyclosilicates beryl and cordierite include water and carbon dioxide molecules in channels formed by the open cavities. Water molecules in the channels have two forms that are distinguished by whether they coordinate to extra-framework cations (type II) or not (type I). We measured polarized infrared (IR) spectra for thin sections of the (100) plane of beryl or the (100) and (010) planes (cb and ca planes) of cordierite under various temperature conditions. The spectral features of major bands clearly showed the distinguishable behavior of types I and II water molecules under high temperature as follows. Over the temperature range from room temperature to 800°C where rapid dehydration did not occur, the decrease in band heights for type II water molecules were smaller than those for type I, and band shifts were more predominant for type II water molecules. The decrease in band heights and band shifts of type I/II bands differed also for beryl and cordierite, which arises from the different ways in which water molecules are fixed in the channels. Dehydration was enhanced at 850°C. The IR spectra at room temperature quenched from 850°C both for beryl and cordierite showed that the vibrational bands related to type II water molecules were stable after those related to type I water molecules disappeared. In addition, frequency changes of type II bands were observed, possibly because of changes of coordination states of type II water molecules to extra-framework cations in the channels.     

Valent state and coordination of cobalt Ions in beryl and chrysoberyl crystals

We have studied the polarized optical absorption and EPR spectra of Co-doped beryls grown by hydrothermal, flux, and gas-transport methods, and chrysoberyl grown by the Czochralski method. In beryls three groups of bands, belonging to three various Co centers, were distinguished by analysis of the absorption band intensities. The first group, bands with maxima at 22 220 (E c), 17 730 (E c), and 9090 (E c), 7520 (E c) cm^–1 are due to Co²⁺ in octahedral site of Al³⁺. The second group is bands at 18 940, 18 250, 17 700 (E c), 18 300, 17 700, 17 000 (E c) and 8830 (E c), 7350 (E c) cm^–1 and 5320 (E c), 3880 (E c) cm^–1, which are caused by Co²⁺ in tetrahedral site of Be²⁺. A weak wide band in flux and gas-transport beryl in the region of 12 500–8300 cm^–1 (E , c) is related to Co³⁺ in octahedral Al³⁺ site. In hydrothermal beryl, bands 13 200 (E c), 10 900 (E c), and 8500 (E c) cm^–1 are caused by an uncontrolled impurity of Cu²⁺ ions. For Co-doped chrysoberyl one type of center of Co has been established: Co²⁺ in the octahedral site of Al³⁺. In the approximation of the trigonal field with regard to Trees correction, the energy levels of Co²⁺ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is explained well in terms of the spin-orbit interaction.     

Coordination and valent state of nickel ions in beryl and chrysoberyl crystals

We have studied the polarized optical absorption and the EPR spectra of Ni-doped beryls grown by hydrothermal, flux and gas-transport methods, and chrysoberyl grown by the Czochralski and flux methods. In beryls, three groups of bands belonging to three various Ni centres were distinguished by analysis of the absorption band intensities. The first group, bands with maximums at 21740 (E ⊥ c), 17240 (E || c) and 9260 (E ⊥ + || c), 7140 (E || + ⊥ c) cm⁻¹, are due to Ni³⁺ in octahedral Al³⁺ site. The second group is bands at 25640 (E ⊥ c), 22220 (E || c) and 13520 (E || + ⊥ c), 13160 (E ⊥+ || c) cm⁻¹ and 8930 (E ⊥ + || c), 7460 (E || c) cm⁻¹, which are caused by Ni²⁺ in octahedral Al³⁺ site. Weak wide bands at 17540 (E ⊥ c), 15500 (E || c) cm⁻¹ and 6580 (E || + ⊥ c), 5950 (E || c) cm⁻¹ are related to Ni²⁺ in tetrahedral Be²⁺ site. The occurrence of Ni ions in Be²⁺ site is proved by the EPR spectra of ^1VNi⁺ in γ-irradiated samples. According to the spectra of optical absorption of Ni-doped chrysoberyl, two types of Ni centres have been established: Ni³⁺ and Ni²⁺ ions in octahedral Al³⁺ sites. From the EPR spectra of the X-ray irradiated crystals BeAl₂O₄: Ni, it follows that 68% of Ni⁺ ions occupy octahedral Al³⁺ sites with mirror symmetry and 32% are in Al³⁺ sites with inversion symmetry. In the approximation of trigonal field with regard to Trees correction, the energy levels of Ni³⁺ and Ni²⁺ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is well explained in terms of the spin–orbit interaction.     

The relationship between the distribution of nitrogen impurity centres in diamond crystals and their internal structure and mechanism of growth

Fifty diamond crystals of different morphological types (octahedra, dodecahedroids, cubes and single tetrahexahedroid) with differing internal structures were examined using methods of cathodoluminescence (CL), anomalous birefringence and local infrared (IR) analysis. The main objective of the study was to examine the regularities of nitrogen impurity distribution in diamond with differing internal structures. Almost all the analyzed octahedra, as well as dodecahedroids with zonal structures and the blocky dodecahedroids, are characterized either by nearly isothermic growth conditions or by a decrease in formation temperature during the crystallization process. In contrast to zoned octahedra and dodecahedroids, dodecahedroids with zonal–sectorial and sectorial internal structures show a notably different distribution of nitrogen defects, with N_tot generally decreasing from crystal cores to marginal areas, and degree of nitrogen aggregation increasing in the same direction. From this, it would follow that in these crystals, the temperature of diamond formation of the outer crystal zones is approximately 40–50 °C higher than that of the inner zones. The same result (15 to 80 °C) was obtained for diamond crystals with cubic habit, which generally show a fibrous internal structure, reflecting normal mechanisms of growth. The anomalous distribution of nitrogen centres in diamond crystals that grew through the normal mechanism, with a high rate of growth and in an oversaturated medium, might point to non-equilibrium relationships between the concentrations of different nitrogen centres. It is likely that in crystals of this type, the rate of growth is higher than the rate of structural nitrogen aggregation. Thus, it appears that in these peculiar crystals of diamond we deal with non-equilibrium concentrations of nitrogen B centres and, consequently, with anomalous, non-actual diamond formation temperatures.     

Partitioning of iron and magnesium between crystals and partial melts in peridotite upper mantle

The iron-magnesium distribution coefficient, $$K'_D = (X_{\Sigma {\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{\Sigma {\text{FeO}}} )^{{\text{liquid}}} ,$$ has frequently been used as a means of testing whether experimental and natural silicate liquids could have been in equilibrium with olivine of mantle composition. It is shown here that this K′ _D decreases with increasing oxygen fugacity (xxx) for a hydrous partial melt in equilibrium with a natural spinel peridotite assemblage under pressure and temperature conditions corresponding to those of the upper mantle (from 0.52 at the xxx of the iron-wüstite buffer to 0.04 at the xxx of the magnetite-hematite buffer). K′ _D also increases with increasing pressure, with decreasing temperature, and probably with increasing Mg/(Mg+∑ Fe) of the parental peridotite, suggesting that $$K_D = (X_{{\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{{\text{FeO}}} )^{{\text{liquid}}}$$ also increases with increasing pressure and decreasing temperature. Thus, unless these four variables (P, T, xxx, silicate composition) are known for a natural magma, K′ _D and probably K _D are variables, and the Mg/(Mg+∑ Fe) of such a magma cannot be correlated to that of the parent. The K _D determined at 1 atm pressure by Roeder and Emslie has frequently been used to test whether the Mg/(Mg+∑ Fe) ratios of experimentally formed liquids at high pressure in equilibrium with olivine of known Fo content represent the equilibrium Mg/(Mg+Fe²⁺) of this liquid, assuming that ∑Fe=Fe²⁺ and that K′ _D does not vary with P, T, and composition of the system. Published data demonstrate that the oxygen fugacities of the experimental designs employed by different laboratories vary between those of the magnetite-hematite and magnetite-wüstite buffers (6 orders of magnitude), resulting in K′ _D between 0.04 and 0.31 at 1050° C and 15 kbar, for example. Thus, published arguments as to whether the quenched liquids represent equilibrium compositions based on iron-magnesium partitioning are inadequate. The effects of P, T, xxx, and the composition of the starting material must also be considered.     

Sequential growth of cordierite and andalusite porphyroblasts, Cooma Complex, Australia: microstructural evidence of a prograde reaction

Abstract Low-pressure prograde metamorphism of pelitic rocks in the Cooma Complex, south-east Australia, has produced cordierite-andalusite schists at intermediate grades. The first foliation (S₁) is preserved largely as inclusion trails in cordierite porphyroblasts. Microstructural evidence indicates that the cordierite porphyroblasts grew during the early stages of development of a crenulation-foliation (S₂) and that andalusite porphyroblasts grew during the development of a later crenulation-foliation (S₃). Microstructural evidence also indicates that the andalusite was a product of the prograde reaction: cordierite + muscovite ± andalusite + biotite + quartz. The occurrence of the products of this reaction in 'beard'structures between cordierite microboudins formed by extension in S₃ confirms that the andalusite grew during the development of S₃. The investigation shows that porphyroblast-matrix relationships can preserve the orientation of an early S-surface that has been largely obliterated from the matrix, as well as providing relatively direct evidence of sequential mineral growth and metamorphic reactions.     

Model of nucleation and growth of crystals in cooling magmas

The nucleation and growth of liquidus phases in cooling magmas at constant rates are modeled taking into account homogeneous nucleation, diffusion-limited growth, and depletion of crystallizing component from melt, and the temperature-dependent diffusivity. The formulation of governing equations shows that four dimensionless parameters, whose physical meanings are the nucleation difficulty, the fusion enthalpy, the ratio of the growth rate to the cooling rate, and the activation energy of diffusion, control the crystallization phenomena. The nucleation behavior with time (or temperature) is determined primarily by the competition between increasing nucleation rate with cooling and the reduced supersaturation with depletion by progressive growth of crystals previously nucleated. The maximum nucleation rate and the number density of crystals increase with decreasing interfacial tension and diffusivity, and with increasing fusion enthalpy and cooling rate. Quantitative expressions of the time or temperature interval for which the nucleation remains appreciable, the peak nucleation rate, the number density of crystals and the mean crystal radius are derived as functions of controlling parameters, and can be used to estimate the cooling rate or other unknown parameters from the number density of crystals of a rock.     

Physicochemical Conditions of the Formation of Beryl and Aquamarin in Mufushan Granopegmatite Deposit,Hunan Province,China

The formation of the Mufushan granopegmatite was closely related to the Late Yenshanian multiphase and multistage magmatic activities,More than one generation of beryl and aquamarine occur in different types of pegmatite in the granites.The presence of melt and melt-fluid inclusions strongly indicates a melt-solution character of the pegmatitic magma.Forming temperatures of the different generations of beryl in a Na^ -K^ ,Ca^2 -CO3^2--Cl^--SO4^2- solution ranges from 990℃to 200℃.Aquamarine was formed at 720-180℃.The contents of alkali metals(Na^ K^ )in th ore-formming solution of aquamarine are lower than those in the beryl,but the contents of alkali earths(Ca) and salinity are higher,The granite was generated by remelting of the basement formation(meta-sedimentary rocks of the Lengjiaxi Group)which also served as the source of ore-forming material.Beryllium in the pegmatite was transported mainly in the form of Na[Be(CO3)2],with part of it being complexed with Cl^- and SO4^2-.During the generation and evolution of the pegmatite,equilibrium might have been reached in the solid-melt-fluid or solid-fluid system.The intergranular solutions may have reacted with the early crystallized minerals,resulting in potash-feldsparization,albitization and muscovitization during which the ore-forming elements were mobilized and transported in favour of ore deposition.     

东秦岭卢氏稀有金属伟晶岩的绿柱石矿物学特征及其指示意义

绿柱石是重要的铍矿石矿物,记录了花岗伟晶岩型稀有金属矿床的成岩成矿过程。东秦岭伟晶岩区是我国重要的稀有金属产地之一。本文调查了东秦岭卢氏伟晶岩区中的南阳山矿区(703号脉锂矿化伟晶岩和302号脉铍矿化伟晶岩)、七里沟-前台矿区(前台锂矿化伟晶岩)、蔡家沟矿区(大西沟和韭菜沟锂矿化伟晶岩)和瓦窑沟矿区(西山沟和瓦窑沟铍矿化伟晶岩)的伟晶岩内部结构分带,认为东秦岭稀有金属伟晶岩主要为过铝质LCT型伟晶岩,属于稀有金属(REL)类REL-Li亚类。其中,703号脉、韭菜沟和大西沟伟晶岩属复杂型锂辉石亚型,前台伟晶岩属钠长石-锂辉石型,302号脉、瓦窑沟和西山沟伟晶岩属绿柱石型绿柱石-铌铁矿亚型。电子探针结果表明绿柱石富碱金属,贫铁和镁。绿柱石元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。西山沟和瓦窑沟绿柱石的替代机制分别是Na(Fe~(2+),Mg)_(-1)Al_(-1)和NaLi_(-1)Be_(-1)。302号脉、前台、大西沟和韭菜沟绿柱石的替代机制为(Na,Cs) Li_(-1)Be_(-1)。703号脉绿柱石的替代机制包括NaFe~(2+)_(-1)Al_(-1)、NaCs_(-1)和(Na,Cs)Li_(-1)Be_(-1)。绿柱石的Cs2O含量和Na/Cs值揭示伟晶岩分异演化程度序列(由低至高)为瓦窑沟矿区→302号脉铍矿化伟晶岩→蔡家沟矿区→前台→703号脉锂矿化伟晶岩。铍矿化伟晶岩岩浆分异演化程度低于锂矿化伟晶岩岩浆。背散射图像显示绿柱石内部分带多样,包括均一结构、条带状、正/反蚀变边、补丁分带和复杂不规则分带。与铍矿化伟晶岩相比,锂矿化伟晶岩产出的绿柱石内部分带复杂多样,反映更为强烈的液相不混溶和交代作用。随伟晶岩岩浆分异演化程度升高,绿柱石FeO含量降低,内部分带更为复杂,发育蚀变边结构、补丁分带和不规则分带等。绿柱石FeO含量和内部分带特征可作为花岗伟晶岩分异演化程度的潜在指示标志。锂矿化伟晶岩中绿柱石的化学组成和内部分带特征表明岩浆就位时是高度分异演化的稀有金属伟晶岩岩浆。大西沟、韭菜沟和前台锂矿化伟晶岩岩浆就位后未经历明显分异演化过程,而南阳山703号脉伟晶岩岩浆就位后经历了较充分的分异演化,导致稀有金属的进一步富集。锂矿化伟晶岩的稀有金属成矿机制是结晶分异和液相不混溶。     

Chemographic relationships of biotite and cordierite in the McGerrigle thermal aureole, Gaspé, Quebec

Abstract Biotite and cordierite occur in a 1-km wide zone of pelitic hornfelses around the McGerrigle pluton. These phases display systematic changes in X _Fe that can be attributed to continuous reactions involving chlorite or andalusite in the system KFMASH. Through much of the zone biotite and cordierite were products of the 'breakdown'of chlorite. Close to the pluton this continuous reaction was terminated by a discontinuous reaction that introduced andalusite. Pelites which interdigitate with apophyses of the intrusive at the pluton margin contain assemblages that record a continuous reaction between biotite, cordierite, andalusite, muscovite, and quartz or, alternatively, the discontinuous breakdown of muscovite and quartz to K-feldspar and andalusite.
The mole fraction of Fe in biotite and cordierite increased significantly with the progress of the first continuous reaction and apparently decreased during the second continuous reaction. The K _D of Fe-Mg between the minerals decreased and apparently increased, respectively, during the two reactions.
Biotite-cordierite-chlorite assemblages are interpreted to have been stable at temperatures between 525° C and 615° C and biotite-cordierite-andalusite assemblages stable at temperatures between 615° C and 635° C. The confining pressure was estimated to have been < 2 kbar.
The results of this study suggest that the K _D of Fe-Mg between biotite and cordierite is a function of temperature, the Fe-Mg exchange characteristics of the controlling continuous reaction and non-ideal mixing of Fe and Mg.     

Morphology and growth of aragonite crystals in hot-spring travertines at Lake Bogoria, Kenya Rift Valley

Pseudohexagonal aragonite crystals are common components in some hot-spring travertines at Chemurkeu on the western shore of Lake Bogoria, Kenya. Beds, lenses and pods of aragonite crystals are intercalated with beds of white non-crystallographic calcite dendrites. The pseudohexagonal aragonite crystals, which are up to 4 cm long and 4 mm wide, are formed of nested skeletal crystals. Each skeletal crystal is formed of cyclical twinned crystals that are constructed of stacked subcrystals. The latter are inclined at a consistent angle of 40° to the long axis of the pseudohexagonal aragonite crystal. Intense competition for space during growth modified the crystal morphology with the result that many of the pseudohexagonal crystals are distorted. Intercrystalline and intracrystalline pores are filled or partly filled by epitaxial aragonite overgrowths and/or reticulate microbial coatings that have a high concentration of Si and Mg. In places, this extracellular mucus induced etching of the underlying aragonite crystal. Today the hot (T>95 °C) Na-HCO₃-Cl spring waters at Chemurkeu have a salinity of 5–6 g L^?1 TDS, a pH of 8·1–9·1, Ca²⁺ concentrations of <2 mg L^?1 and Mg²⁺ concentrations of <0·7 mg L^?1, The springs of the Lake Bogoria Geothermal Field are fed by a shallow aquifer (T～100 °C) and a deeper aquifer (T～170 °C). Springs at Chemurkeu derive from meteoric groundwater, lake water and condensed steam, and are fed mainly from the shallow thermal aquifer. Much of the aragonite may have formed when the spring waters contained more dissolved Ca²⁺ than today, possibly under more humid conditions during the Holocene.     

EPR investigation of the methyl radical,the hydrogen atom and carbon oxide radicals in Maxixe-type beryl

The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1 signal typical for the CH₃ radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g _// = 2.00263, g _⊥ = 2.00249 and A_// = 2.288 mT, A_⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A ₀ = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g _// = 2.00265, g _⊥ = 2.00625 and A_// = 0.895 mT, A_⊥ = 0.885 mT, could come from a HCO₃ radical. One narrow and easily saturated signal with g _// = 2.00227 and g _⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g _// = 2.0017 and g _⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise from a carbon dioxide radical, which rotates around its symmetry axis.     

Distribution and significance of cordierite in paragneisses of the Hudson Highlands,southeastern New York

Cordierite occurs locally and sporadically in biotite-quartz-two feldspar paragneisses of the Precambrian Highlands complex in southeastern New York. Cordieritic and associated non-cordieritic gneisses were compared to determine the significance of cordierite for the metamorphic history of the complex.Microprobe analyses of the ferromagnesian phases show the following ranges in Fe/Mg (mol.): cordierite 0.19–0.43; biotite 0.33–0.73; garnet 1.98–3.56. Feldspar compositional ranges are: plagioclase An_25–53; K-feldspar in microperthite Or_62–87Ab_12–37 An_0–1. Garnet and plagioclase associated with cordierite are depleted in Ca relative to those in cordierite-free assemblages.Textural evidence, phase rule considerations and consistent distribution coefficients for FeO and MgO in coexisting garnet, cordierite and biotite from each locality examined suggest that all phases formed in at least local equilibrium during the hornblende-granulite subfacies metamorphism. The assemblages studied limit the conditions of metamorphism to between 700 and 750° C and 3.0 to 5.5. Kb. total pressure, with P _T greater than . Differences in mineral compositions and partitioning coefficients among the sampled areas suggest slight local differences within these ranges.Mineral and modal analyses of cordierite-bearing and cordierite-free gneisses show the latter to be enriched in calcium and potassium and depleted in alumina relative to the former. We conclude that the rarity of cordierite in the Highlands paragneisses reflects a scarcity of parent rocks of suitable composition rather than unfavorable physical conditions.     

Growth of cordierite in the Archean metasediments near Yellowknife,district of Mackenzie,Canada

The widespread occurrence of cordierite in the Archean metasediments near Yellowknife was attributed by earlier workers to the contact metamorphism associated with the granite. However, detailed field and textural studies on the cordierite-bearing rocks near Sparrow Lake indicate that the growth of cordierite is not restricted to the aureole around the Sparrow Lake granite. Fabric relations demonstrate that cordierite grew under regional metamorphic conditions existing before and after the intrusion of the granite. Emplacement of the Sparrow Lake pluton is considered to represent the culmination stage of regional tectonism that manifested itself as deformation, metamorphism and granite intrusion in the Sparrow Lake area.

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Zusammenfassung Die Verbreitung von Cordierit in den archaischen Metasedimenten bei Yellowknife führten frühere Autoren auf die mit dem Granit verbundene Kontaktmetamorphose zurück. Genaue Gelände- und Strukturuntersuchungen an den cordieritführenden Gesteinen aus dem Gebiet von Sparrow Lake zeigen jedoch, daß das Wachsen von Cordierit nicht auf die Aureole um den Sparrow Lake-Granit beschränkt ist. Gefüge-Beziehungen beweisen, daß Cordierit unter regionalen metamorphen Bedingungen gebildet wurde, die vor und nach der Intrusion des Granits herrschten. Die Bildung des Sparrow Lake-Plutons wird als Höhepunkt regionaler tektonischer Vorgänge angesehen, die im Sparrow Lake-Gebiet als Deformation, Metamorphose und Granitintrusion in Erscheinung traten.

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Résumé L'extension de la cordiérite dans les métasédiments archéens de la région de Yellowknife fut longtemps attribuée au métamorphisme de contact associé au granite. Cependant des études précises sur le terrain et l'examen de la texture des roches à cordiérite indiquent que la croissance de la cordiérite n'est pas restreinte à l'auréole du granite du lac Sparrow. Les relations vectorielles démontrent que la croissance de la cordiérite s'est effectuée dans des conditions métamorphiques régionales existant avant et après l'intrusion du granite. La mise en place du pluton du lac Sparrow réprésenterait donc l'étape culminante de la tectonique régionale qui dans la région du lac Sparrow s'est manifestée par la déformation, le métamorphisme et l'intrusion granitique.

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, . Yellowknife , Sparrow-Lake. , , . Sparrow-Lake , , , .

     

Energetics of hydration of cordierite and water barometry in cordierite-granulites

The Gibbs free energy and volume changes attendant upon hydration of cordierites in the system magnesian cordierite-water have been extracted from the published high pressure experimental data at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P _total, assuming an ideal one site model for H₂O in cordierite. Incorporating the dependence of ΔG and ΔV on temperature, which was found to be linear within the experimental conditions of 500°–1,000°C and 1–10,000 bars, the relation between the water content of cordierite and P, T and \(f_{{\text{H}}_{\text{2}} {\text{O}}} \) has been formulated as $$\begin{gathered} X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} = \hfill \\ \frac{{f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }}{{\left[ {{\text{exp}}\frac{1}{{RT}}\left\{ {64,775 - 32.26T + G_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{1, }}T} - P\left( {9 \times 10^{ - 4} T - 0.5142} \right)} \right\}} \right] + f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }} \hfill \\ \end{gathered} $$ The equation can be used to compute H₂O in cordierites at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) <1. Our results at different P, T and partial pressure of water, assuming ideal mixing of H₂O and CO₂ in the vapour phase, are in very good agreement with the experimental data of Johannes and Schreyer (1977, 1981). Applying the formulation to determine \(X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} \) in the garnet-cordierite-sillimanite-plagioclase-quartz granulites of Finnish Lapland as a test case, good agreement with the gravimetrically determined water contents of cordierite was obtained. Pressure estimates, from a thermodynamic modelling of the Fe-cordierite — almandine — sillimanite — quartz equilibrium at \(P_{{\text{H}}_{\text{2}} {\text{O}}} = 0\) and \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P_total, for assemblages from South India, Scottish Caledonides, Daly Bay and Hara Lake areas are compatible with those derived from the garnetplagioclase-sillimanite-quartz geobarometer.     

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.     

不同类型铍矿床中绿柱石的地球化学特征及其地质意义

绿柱石是稀有金属铍最重要的载体矿物, 开展绿柱石系统的矿物学和地球化学研究对查明铍成矿条件和机制从而指导找矿具有重要意义。本文利用电子探针、LA-ICP-MS等技术手段, 对我国不同地区不同类型铍矿床中的绿柱石开展了地球化学研究, 结果表明, 伟晶岩型、岩浆热液型铍矿床中绿柱石的主要成分BeO、Al₂O₃、SiO₂含量基本相当, 还含碱金属元素Na、Li、Cs、Rb和铁镁质元素Fe、Mg、Ca等, 两种绿柱石中MgO和Cr₂O₃含量差异较大。伟晶岩型绿柱石的Al位类质同象置换程度低于岩浆热液型绿柱石, 其组分差异与成矿温度、压力和结晶介质等因素有关, 伟晶岩型绿柱石结晶于黏度高的熔体, 高温高压使Al₂O₃活度增强, 岩浆的固相线温度降低, 使得Be以络合物的稳定形式迁移并沉淀, 不易携带外来元素; 浆热液型绿柱石结晶于粘度低、流动性更好的热液流体中, 温度和压力较低不足以形成稳定的络合物, 导致体系中元素分散, 且热液对成矿元素的溶解度更高, 易于与围岩发生强烈的交代反应产生元素置换。绿柱石中离子类质同象置换产生的Fe、Cr、V和Mg导致绿柱石呈现不同色调和亮度的绿色, 其中Mg可能是致翠绿色的原因之一; 伟晶岩型铍矿床中更可能形成富铬型绿柱石, 岩浆热液型铍矿床中更可能形成富钒型绿柱石, 也可能形成富铬型绿柱石, 推测是由于岩浆热液易于与围岩发生蚀变反应, 使基性岩-超基性岩中的Cr, 或变沉积岩中的V进入绿柱石结晶介质而形成祖母绿。本文提供了两种区分伟晶岩型和岩浆热液型绿柱石的指标, 即绿柱石Na/Li值一定程度上呈现出伟晶岩型绿柱石小于岩浆热液型的特征; Rb-Cs图解中由两条趋势线(岩浆热液型K₁=1.257, 伟晶岩型K₂=0.015)限定的I区(K≥1.257)多为岩浆热液型绿柱石, Ⅲ区(K≤0.015)多为伟晶岩型绿柱石。绿柱石的Mg-Cr组分多受到碳酸盐组的影响, 翠绿色绿柱石多形成于碳酸盐岩赋矿或含碳酸盐矿物的矿脉中。本次研究的伟晶岩绿柱石样品所处矿床多赋存于变泥质岩中, 形成环境缺乏碳酸盐类矿物, 今后应注意在赋存于碳酸盐岩中的伟晶岩脉中寻找祖母绿。