An experimental study of the effect of boron on a water saturated haplogranite at 1 Kbar vapour pressure

An experimental study of the effect of boron in the water saturated Q-Or-Ab-B₂O₃-H₂O system has been performed at P=1 Kbar to provide experimental data and explain the role of boron in some late magmatic and early hydrothermal events. Experiments were conducted between 500° C and 800° starting from a gel, or a previously crystallized gel, and variable amounts of boron (0 to 18% B₂O₃) added to water. The phases obtained were: quartz, sanidine, albite, silicate liquid quenched to glass, and aqueous vapour phase. Boric acids, borates and isotropic low index materials were found in the quenched vapour phase. An aluminium silicate-like mineral, not yet fully identified, is also present.The solidus temperature of the Q-Or-Ab composition is lowered by 60° C when 5 wt. % B₂O₃ is added and by more than 130° C when 17wt. % B₂O₃ is added. Compositions of equilibrated silicate melts and vapours were obtained between 780° C and 750° C for various B₂O₃ concentrations. The vapour phase is B and Si rich. It is also enriched in Na with respect to K, and in alkalis with respect to Al. Its silicate solute content is higher than in experiments with pure water. The solubility of water is increased by the addition of boron in Q-Or-Ab melts. Microprobe data show that the melts equilibrated with vapour phases become hyperaluminous and more potassic than sodic. The partition coefficient of boron is in favour of the vapour (k _D=B₂O₃% in melt/B₂O₃% in vapour=0.33±0.02). The effect of the interaction between the silicate phases and the vapour is discussed. Comparison is made between the behaviour of boron and that of chlorine and fluorine. Geological applications are also provided, which concern the influence of boron on minimum melting, on muscovite stability and on the hypersolvus-subsolvus transition.     

Coordination of boron in nominally boron-free rock forming silicates: Evidence for incorporation of BO3 groups in clinopyroxene

To explore mechanisms of B-incorporation in common chain silicates we have investigated synthetic diopside samples produced under boron-saturated conditions by ¹¹B and ²⁹Si magic-angle spinning (MAS) NMR and single-crystal NRA, FTIR, EMP and XRD/SREF techniques. Our samples contain 0.14-0.65 wt.% B₂O₃. NMR reveals that B is predominantly present in trigonal coordination in the clinopyroxene structure. This observation is supported by vibrational bands characteristic for B-O stretching in BO₃ groups in the range 1250-1400 cm⁻¹ in polarised single crystal FTIR-spectra. Single crystal structure refinements suggest that boron replaces Si at the T site. Combined, these results suggest that boron replacement for Si at the T-site leads to disruption of one of the T-O bonds of the nominal clinopyroxene structure resulting in replacement of SiO₄ tetrahedra by BO₃ groups. Our results show that high concentrations of boron can be incorporated in the nominally boron-free diopside. Elevated B-concentrations in the present calcic clinopyroxenes are accompanied by modifications of the diopside crystal structure involving the breaking of one T-O bond and simultaneous formation of vacancies at the octahedral M2 site. These structural modifications destabilize the structure and constitute thereby limiting factors for incorporating higher boron concentrations in diopside.     

Melt/biotite B/B isotopic fractionation and the boron local environment in the structure of volcanic glasses

This paper is focused on the role of boron coordination in determining the ¹¹B/¹⁰B isotopic fractionation between melt/glass and biotite at magmatic temperatures. For this purpose, three evolved volcanic rocks from Roccastrada, Mt. Amiata, and Mt. Cimini belonging to the Neogene-Quaternary magmatism of central Italy were studied. In these samples, the measured boron biotite-glass partition coefficient ranges between 0.004 and 0.011, indicating that boron behaves as an incompatible element during biotite crystallization. The ¹¹B magic-angle spinning nuclear magnetic resonance (NMR) spectra reveal the presence of trigonal BO_3/2 units, tetrahedral BO_4/2⁻ sites, and three-coordinated BO_2/2O⁻ species containing one nonbridging oxygen. The relative contributions of these different boron sites were estimated by spectral deconvolution, and it was observed that the fraction of trigonally coordinated boron decreases with increasing K₂O concentration in the glass. The ¹¹B/¹⁰B isotopic fractionation between biotite and melt/glass was observed to be large even at magmatic temperatures and was found to be 1.0066 (Roccastrada sample), 1.00535 (Mt. Amiata sample), and 1.00279 (Mt. Cimini sample). Fractionation is mostly related to the relative amount of trigonal and tetrahedral boron sites in the glass network rather than to other processes, including the speciation of hydrous species in the glass structure. The measured α values are significantly higher than the calculated ones obtained using the reduced partition function ratios (RPFRs) for B(OH)₃ and B(OH)₄⁻ as reported by Kakihana et al. (1977) and the abundance of trigonal and tetrahedral boron obtained by ¹¹B NMR spectra. Furthermore, a nonlinear relationship is observed between the percentage of BO₄ in the glass structure and the measured 1000lnα, suggesting that the approximation of monomeric B(OH)₃ and B(OH)₄⁻ species contributions through ideal mixing in calculating the RPFRs in polyanions (Oi et al., 1989) probably does not apply to silicate glasses.The large B isotopic fractionation measured between glass and biotite and its dependence on the boron coordination in the glass are a limitation to the use of δ¹¹B in the mineral to characterize magmas. Nonetheless, the high incompatible behavior of boron in the most common magmatic minerals rules out that fractional crystallization significantly modified the B isotopic composition of the melt.     

Boron incorporation into mullite

Summary Boron-doped mullites were synthesized using aluminium nitrate-nonahydrate, tetraethoxysilane and boric acid in a sol–gel process with subsequent annealing at 950 and 1300 °C for five hours. Two different bulk compositions with constant Al₂O₃ contents (60 and 70 mol%, respectively) and varying SiO₂ plus B₂O₃ contents were investigated. X-ray powder diffraction analyses yielded a linear decrease of the lattice parameters with increasing bulk B₂O₃ content, which was interpreted as to be due to boron incorporation. Related to the increasing boron content, corresponding infrared spectra revealed a slight and continuous shift for most of the absorption bands. These data show that mullite is able to incorporate large amounts of boron into its structure (up to about 20 mol% B₂O₃ depending on the bulk composition of the starting materials). Infrared analyses suggest that boron is incorporated into the mullite structure in form of planar three-fold coordinated BO₃ groups. Author’s address: A. Beran, Institut für Mineralogie und Kristallographie, Universit?t Wien-Geozentrum, Althanstra?e 14, 1090 Wien, Austria     

High-pressure synthesis,long-term stability of single crystals of diboron trioxide,B<Subscript>2</Subscript>O<Subscript>3</Subscript>, and an empirical electronic polarizability of <Superscript>[3]</Superscript>B<Superscript>3+</Superscript>

Single crystals of B₂O₃ are needed for the precise determination of the refractive indices used to calculate the electronic polarizability α of 3-coordinated boron. The α(B) values in turn are used to predict mean refractive indices of borate minerals. Since the contribution of boron to the total polarizability of a mineral is very low, the synthetic compound B₂O₃ represents an ideal model system because of its high molar content of boron. Millimeter-sized crystals were synthesized at 1 GPa in a piston-cylinder apparatus. The samples were heated above the liquidus (800 °C), subsequently cooled at 15 °C/h to 500 °C and finally quenched. The refractive indices were determined by the immersion method using a microrefractometer spindle stage. The refractive indices n _o = 1.653 (3) and n _e = 1.632 (3) correspond to a total polarizability for B₂O₃ of α = 4.877 Å³. These values were used to determine the electronic polarizability of boron of α(B) = 0.16 Å³. Although the surface of the B₂O₃ crystals was coated with a hydrous film immediately after being exposed to air, its bulk crystallinity is retained for a period of at least 2 months.     

电感耦合等离子体发射光谱法测定硼硅酸盐玻璃中的硼等常见元素

硼硅酸盐玻璃中的硼、钙、镁、铝、铁、钛、硅等常见元素普遍采用各元素分别测定的方式进行分析,分析效率很低;而且硼的测定普遍采用容量法,当B2O3含量低于1%时,容量法测定误差较大。本文以KOH熔融的方式消解样品,采用电感耦合等离子体发射光谱法(ICP-AES)进行分析。通过实验研究了KOH用量和不同称样量对B2O3测定结果的影响。结果表明,KOH用量在3 g以上时有较好的熔样效率和熔样效果,称样量低于0.4 g对B2O3测定结果无明显影响,考虑到其他元素的测定,确定了KOH用量优选3 g,称样量优选0.1 g。在此条件下,测定B2O3等常见元素的精密度(RSD,n=6)≤2%,加标回收率在96.0%~105.6%之间,除Si O2测定误差较大外,其他元素的测定结果均令人满意。本方法确定的B2O3的定量限为0.067%,且对于B2O3最高含量达到16%的测定结果也令人满意,因此可测定B2O3含量的范围至少为0.067%~16%。当样品中的B2O3含量高于4%时,方法准确度和精密度与国家标准分析方法(容量法)相当;当B2O3含量低于1%时,方法准确度和精密度都优于容量法。与现有报道相比,本方法显著拓宽了B2O3的测定范围,并具有良好的准确度,而且在B2O3准确测定的同时,也实现了Ca、Mg、Al、Fe、Ti的定量分析和Si的半定量分析,大大提高了分析效率,可以实现硼硅酸盐玻璃中B2O3等常见元素的准确快速分析。     

Boron in granitic magmas: stability of tourmaline in equilibrium with biotite and cordierite

Experiments at 750 °C, 200 MPa_(H2O), a _(H2O)=1, and fO₂∼Ni-NiO established that the equilibrium among tourmaline, biotite, cordierite, and melt (± spinel, aluminosilicate, or corundum) occurs with ∼2 wt% B₂O₃ in strongly peraluminous melt with an aluminosity, measured by the parameter ASI, of >1.2. The experiments demonstrate the relationship of tourmaline stability to the activity product of the tourmaline components boron and aluminum, which are inversely related to one another. Tourmaline is unstable in metaluminous to mildly peraluminous melts (ASI <1.2) at 750 °C regardless of their boron content. For a given aluminosity, addition of components such as F requires a greater boron content of melt at this equilibrium. The stability of tourmaline increases with decreasing temperatures below 750 °C. At the inception of melting, tourmaline breaks down incongruently to assemblages containing crystalline AFM silicates (biotite, cordierite, garnet, sillimanite), aluminates (spinel, corundum), and B-enriched but Fe-Mg-poor melt. Granitic melts are likely to be undersaturated in tourmaline from the start of their crystallization, and their initial boron contents will be limited by the abundance of tourmaline in their source rocks. Quartzofeldspathic (gneissic, metapelitic) rocks that reached conditions of the granulite facies and still contain (prograde) tourmaline are rare, and probably have never yielded a partial melt. Most leucogranitic magmas will initially crystallize biotite, cordierite, or garnet, but not tourmaline. With crystallization, the Fe-Mg content of melt decreases, and the B₂O₃ content increases until the tourmaline-biotite and/or tourmaline-cordierite (or garnet) equilibria are attained. The B₂O₃ content of melt is buffered as long as these equilibria continue to operate, but low initial Fe-Mg contents of the magmas limit the quantity of boron that can be consumed by these reactions to <1 wt% B₂O₃. Normally, leucogranitic magmas contain insufficient Fe and Mg to conserve all boron as tourmaline and thus lose a large fraction of magmatic boron to wallrocks. Leucogranites and pegmatites with tourmaline as an early and only AFM silicate mineral probably contained >2 wt% B₂O₃ in their bulk magmas. Received: 6 August 1996 / Accepted: 21 July 1997     

Element partitioning between immiscible borosilicate liquids: A high-temperature centrifuge study

The main objectives of this study were to investigate conditions for stable and metastable liquid immiscibility in dry borosilicate synthetic systems and to evaluate effects of temperature and bulk melt composition on two-liquid element partitioning and boron speciation. To distinguish between the stable immiscibility and quench heterogeneity, we used high-temperature centrifuge phase separation. For the case of stable liquid immiscibility, silica-rich (LS) and borate-rich (LB) conjugate liquids formed two distinct layers separated by a sharp meniscus. The liquids were quenched into glasses, which were analysed by electron microprobe. Some of the glasses were also studied by Raman spectroscopy. We used several synthetic mixtures along the danburite-anorthite (CaB₂Si₂O₈-CaAl₂Si₂O₈) and danburite-reedmergnerite (CaB₂Si₂O₈-NaBSi₃O₈) joins. In addition, we studied four complex, six-component, Mg-bearing compositions with variable Na₂O and Al₂O₃ contents. The experiments show that the width of the LS-LB miscibility gap decreases more rapidly with the B-Al substitution (in the danburite-anorthite join) than with the Ca-Na substitution, implying that interactions between network-forming elements have a greater effect on borate-silicate unmixing than the nature of network-modifying cations. Ca and Mg partition strongly to the depolymerised borate-rich liquid with LB-LS partition coefficients of ∼40 and higher. On the other hand, two-liquid partition coefficients of Na and Al in most cases are close to 1 and show complex variations with temperature and bulk melt composition. Raman spectra of LB glasses quenched at different temperatures suggest that the proportion of trigonal boron in bulk boron content decreases with decreasing temperature. The change in boron speciation appears to affect Al and Na two-liquid partitioning in such a way that at low temperatures, the latter element becomes more compatible with LS.     

EPR study of coordination of Ag and Pb cations in BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals and barium borate glasses

It is shown the possibility to determine the coordination of paramagnetic ions in disordered solid structures, e.g., in barium borate glasses. For this purpose the electron paramagnetic resonance (EPR) method was used to study α-and β-BaB₂O₄ crystals and glasses of 45·BaO × 55·B₂O₃ and 40·BaO × 60·B₂O₃ (mol%) composition activated by Ag⁺ and Pb²⁺ ions. After the samples were exposed to X-rays at 77 K, different EPR centers were observed in them. In α-and β-BaB₂O₄ crystals and glasses the EPR centers Ag²⁺, Ag⁰, Pb⁺, Pb³⁺, and hole centers of O⁻ type were studied. The EPR parameters of these centers and their arrangement in crystal structure were determined. It is shown that Pb³⁺ ions in β-BaB₂O₄ crystals occupy Ba²⁺ position in an irregular polyhedron from the eight oxygen, whereas in α-BaB₂O₄ crystals they occupy Bа₂ position in a sixfold coordination. Pb⁺ ions in α-BaB₂O₄ crystals occupy Bа₁ position in a ninefold coordination from oxygen. In barium borate glasses, Pb³⁺ ions were studied in coordination polyhedron from six oxygen atoms and in a polyhedron from nine to ten oxygen atoms. It is assumed that the established difference in the structural position of Pb³⁺ ions in glasses is due to their previous incorporation in associative cation–anion complexes (AC) and “free” structure-forming cations (FC). Computer simulations have been performed to analyze the stability of specific associative complexes and to compare their bond lengths with experimental data.     

ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide

Boron is an important micronutrient for plants, but high B levels in soils are often responsible for toxicity effects in plants. It is therefore important to understand reactions that may affect B availability in soils. In this study, Attenuated Total Reflectance Fourier transform Infrared (ATR-FTIR) spectroscopy was employed to investigate mechanisms of boric acid (B(OH)₃) and borate (B(OH)₄⁻) adsorption on hydrous ferric oxide (HFO). On the HFO surface, boric acid adsorbs via both physical adsorption (outer-sphere) and ligand exchange (inner-sphere) reactions. Both trigonal (boric acid) and tetrahedral (borate) boron are complexed on the HFO surface, and a mechanism where trigonal boric acid in solution reacts to form either trigonal or tetrahedral surface complexes is proposed based upon the spectroscopic results. The presence of outer-sphere boric acid complexes can be explained based on the Lewis acidity of the B metal center, and this complex has important implications for boron transport and availability. Outer-sphere boric acid is more likely to leach downward in soils in response to water flow. Outer-sphere boron would also be expected to be more available for plant uptake than more strongly bound boron complexes, and may more readily return to the soil solution when solution concentrations decrease.     

Liquid-vapor fractionation of boron and boron isotopes: Experimental calibration at 400°C/23 MPa to 450°C/42 MPa

We experimentally determined the boron partitioning and boron isotope fractionation between coexisting liquid and vapor in the system H₂O−NaCl−B₂O₃. Experiments were performed along the 400 and 450°C isotherms. Pressure conditions ranged from 23 to 28 MPa at 400°C and from 38 to 42 MPa at 450°C. Boron partitions preferentially into the liquid. Its overall liquid-vapor fractionation is, however, weak: Calculated boron distribution coefficients D_B^liquid-vapor are < 2.5 at all run conditions. With decreasing pressure (i.e. increasing opening of the solvus) D_B^liquid-vapor increases along the individual isotherms. Extrapolation to salt saturated conditions yields maximum boron liquid-vapor fractionations of D_B^liquid-vapor = 1.8 at 450°C and D_B^liquid-vapor = 2.7 at 400°C. ¹¹B preferentially fractionates into the vapor. Calculated Δ¹¹B_vapor-liquid = {[(¹¹B/¹⁰B)_vapor - (¹¹B/¹⁰B)_liquid]/(¹¹B/¹⁰B)_{NBS 951}}*1000 are small and range from 0.2 (± 0.7) to 0.9 (± 0.5) ‰ at 450°C and from 0.1 (± 0.6) to 0.7 (± 0.6) ‰ at 400°C. The data indicate increasing isotopic fractionation with decreasing pressure (i.e. increasing opening of the solvus). Extrapolation to salt saturated conditions yields maximum boron isotope liquid-vapor fractionations of Δ¹¹B_vapor-liquid = 1.5 (± 0.7) ‰ at 450°C and Δ¹¹B_vapor-liquid = 1.3 (± 0.6) ‰ at 400°C. The weak boron isotope fractionation suggests similar trigonal speciation in liquid and vapor. Although the boron and boron isotope fractionation between liquid and vapor is only weak, mass balance calculations indicate that for high degrees of fractionation liquid-vapor phase separation in an open system can significantly alter the boron and boron isotope signature of low-salinity hydrous fluids in hydrothermal systems. Comparing the model calculations with natural oceanic hydrothermal fluids, however, indicate that other processes than fluid phase separation dominate the boron geochemistry in oceanic hydrothermal fluids.     

Boron isotopic fractionation between minerals and fluids: New insights from in situ high pressure-high temperature vibrational spectroscopic data

Equilibrium boron isotopic fractionations between trigonal B(OH)₃ and tetragonal B(OH)₄⁻ aqueous species have been calculated at high P-T conditions using measured vibrational spectra (Raman and IR) and force-field modeling to compute reduced partition function ratios for B-isotopic exchange following Urey’s theory. The calculated isotopic fractionation factor at 300 K, α_3/4 = 1.0176(2), is slightly lower than the formerly calculated value of α_3/4 = 1.0193 (Kakihana and Kotaka, 1977), due to differences in the determined vibrational frequencies. The effect of pressure on α_3/4 up to 10 GPa and 723 K is shown to be negligible relative to temperature or speciation (pH) effects. Implications for the interpretation of boron fractionation in experimental and natural systems are discussed. We also show that the relationship between seawater-mineral B isotope fractionation and pH can be expressed using two variables, α_3/4 on one hand, and the pK_a of the boric acid-borate equilibrium on the other hand. This latter value is given by the equilibrium of boron species in water for the carbonate-water exchange, but could be governed by mineral surface properties in the case of clays. This may allow defining intrinsic paleo-pHmeters from B isotope fractionation between carbonate and authigenic minerals. Finally, it is shown that fractionation of boron isotopes can be rationalized in terms of the changes in 1) coordination of B from trigonal to tetrahedral in both fluids and minerals; and 2) the ligand nature around B from OH⁻ in the fluid and some hydrous minerals to non-hydrogenated O in many minerals. Relationships are established that allow predicting the isotopic fractionation factor of B between minerals and fluid.     

A computer simulation study of natural silicate melts. Part I: Low pressure properties

In implementing into a molecular dynamics simulation code a simple interionic potential developed to describe the nine component system K₂O-Na₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ (KNCMFATS), it has been possible to reproduce satisfactorily a number of thermodynamic, structural and transport properties of a representative set of natural silicate melts. An important conclusion reached in this study is the good transferability of the potential from felsic to ultramafic compositions although this transferability becomes less accurate with high silica contents (rhyolitic composition and beyond) and with very iron-rich silicates (e.g. fayalite). A key feature of the simulation is to make the link between macroscopic properties of the melt and its microscopic structure and dynamics. We thus obtain a relationship between the molar volume of the melt, the number of network modifiers and the oxygen coordination number. The simulation also allows one to quantify the coordination environment around the cations as function of the melt composition. Furthermore, the electrical conductivity of the high temperature liquid is investigated.     

Optical absorption spectroscopy of the P213-P212121 transformation in K2Co2(SO4)3 langbeinite

Crystal field spectra have been obtained from K₂Co₂(SO₄)₃ at a number of temperatures from 20 K to room temperature. The transition to the ⁴ T _1g(P) excited state is found to be split at all temperatures owing to the trigonal distortion of the Co site. Below the P2₁3-P2₁2₁2₁ phase transition temperature an excess splitting is observed owing to the additional distortion of the site in the orthorhombic phase. This excess distortion is found to be a linear function of temperature with no first order step at T _c. Thus on a local scale the transition appears to be second order. The trigonal splitting increases with increasing temperature above T_c; this is not expected from the Speer-Salje model of the transition mechanism, which predicted decreasing distortion of the oxygen octahedra with increasing temperature. We propose that the apparent increase of asymmetry is due to the off centring of the Co atom in the high temperature phase in a more regular environment.     

Phase transitions in langbeinites I: Crystal chemistry and structures of K-double sulfates of the langbeinite type M 2 + + K2(SO4)3, M + +=Mg,Ni, Co,Zn, Ca

The crystal structures of the langbeinite type M ₂ ^{+ +} K₂(SO₄)₃ with M ^{+ +}=Mg, Ni, Co, Zn, Ca in their cubic phase (P 2 ₁ 3) and Ca₂K₂(SO₄)₃ in its orthorhombic phase (P 2 ₁ 2 ₁ 2 ₁) are determined. Whereas the SO₄-tetrahedra in these compounds are almost undistorted, the two symmetry-independent coordination polyhedra of M ^{+ +} are highly distorted octahedra with trigonal site symmetry in P 2 ₁ 3. The deformation of the oxygen octahedra and the off-centering of M ^{+ +} along the trigonal axis show systematic dependences on the ionic radii and the electronegativities of the M ^{+ +}-ions. The correlations are remarkably different for the two symmetry-independent M ^{+ +}-ions indicating different M ^{+ +} — O bonding. The octahedral deformations show also linear correlations with the phase transition temperatures (P 2 ₁ 3 — P 2 ₁ 2 ₁ 2 ₁) of the different compounds. This observation leads to a new model for the phase transition mechanism which is based on thermal instabilities of the M ^{+ +} — O and K — O polyhedral distortions. The cubic high temperature phase is characterized by high symmetric oxygen coordinations around M ^{+ +} which distort with decreasing temperature. At T _c the trigonal site symmetry is broken in such a way that the K — O coordination becomes denser at the expense of a wider and less symmetric M ^{+ +} — O coordination.     

Effect of the <Emphasis Type="Italic">d</Emphasis> electrons on phase transitions in transition-metal sesquioxides

We present a systematic density-functional study of phase relations in three 4d-transition-metal sesquioxides: Y₂O₃, Rh₂O₃, and In₂O₃. Y₂O₃ and In₂O₃ undergo pressure-induced transitions to phases with larger cation coordination number (from 6 to 7) at low pressures. However, this does not occur in Rh₂O₃ at least up to ~300 GPa. This cannot be explained by usual arguments based on ionic-radii ratios often used successfully to explain phase relations in simple-metal and rare-earth sesquioxides and sesquisulfides. Inspection of their electronic structures shows that, in Rh₂O₃, the electronic occupancy of 4d orbitals, 4d ⁶, plays a fundamental role in the extraordinary stability of the Rh₂O₃(II)-type phase with respect to coordination increase. We point out that d-orbital occupancy is a fundamental factor in explaining phase relations in transition-metal sesquioxides and sesquisulfides.     

Synthesis and crystal chemistry of kornerupine in the system MgO-Al2O3-SiO2-B2O3-H2O

Boron-bearing kornerupine was synthesized in the simplest possible model system at fluid pressures and temperatures both within and outside the stability field of boron-free kornerupine. Best conditions for synthesis of single-phase products are 7 kb and 830 °C. Microprobe and wet chemical analyses as well as X-ray studies indicate compositional variations of kornerupines regarding all five constituent components: Increasing B-contents (from 0.37 to 3.32 wt% B₂O₃) are correlated with decreasing OH^? values largely according to the Eq. B³⁺?3 H⁺; the ratio MgO∶Al₂O₃∶SiO₂ varies from 4∶3∶4 in the direction towards 1∶1∶1. Thus kornerupine exhibits an at least ternary range of solid solution in the system studied. Crystallochemically speaking it is significant that, although the Mg∶Al∶Si ratio of kornerupine may remain constant with increasing boron contents, the total number of cations per formula unit increases beyond the ideal number of 14.0 as given by Moore and Bennett (1968). Considering the presence of an additional structural site at (000) it is suggested that the introduction of boron initiates a sequence of substitutions such as $$B^{[4]} \to Si^{[4] } \to A1^{[4]} \to Mg^{[6]} \to \square$$ . The filling of this site, empty in boron-free kornerupine, by Mg is connected with a loss of hydrogen located near this site. Petrologically speaking an exchange reaction relation exists between kornerupine and its coexisting fluid according to the equation Boron-free kornerupine+B₂O₃=boron-kornerupine+H₂O. The molar fractions $$X_{B_2 O_3 } = B_2 O_3 /\left( {B_2 O_3 + H_2 O} \right)$$ of kornerupines exceed those of their coexisting fluids by about one order of magnitude. Fluids with relatively low X_{B 2 O 3} lead to the coexistence of kornerupine with boron-free minerals such as enstatite and sapphirine, fluids with relatively high X_{B 2 O 3} produce the boron-minerals grandidierite, sinhalite, and tourmaline (in the present system without Na!) in addition to kornerupine.     

湘南地区芙蓉锡矿床中硼矿化的发现及意义

硼矿是中国重要的紧缺矿产,长期依赖进口,找寻新的硼矿资源迫在眉睫.笔者在湘南地区芙蓉锡矿床新发现了矽卡岩型硼矿化,硼矿物包括硼镁铁矿、遂安石和氟硼镁石,1件典型样品的X射线粉晶衍射分析结果表明硼矿物总含量达到47.4％,换算成w(B)(以B2O3计)约为9.5％,高于5％的硼矿最低工业品位.该发现预示着湘南地区,乃至华南与高分异花岗岩有关的钨锡多金属矿集区有良好的硼成矿潜力,在今后的找矿过程中,需加强与钨锡多金属共伴生的硼矿化评价工作.     

Characterization of the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses

X-ray absorption spectroscopy using synchrotron radiation has been applied to the investigation of the coordination geometries around Y, Zr and Nb atoms in metamict zircon, gadolinite, fergusonite, euxenite and samarskite. EXAFS and XANES spectra of their crystalline counterparts and synthetic compounds including ZrO₂, Y₂O₃, YNbTiO₆, YNbO₄, LiNbO₃, and NiNb₂O₆ were also measured for comparison. Metamict zircon shows a significant decrease in its Zr-O bond distances accompanying an increase in distortion of the Zr-O coordination polyhedra as compared with crystalline zircon. On the contrary, the average Nb-O bond distances and the symmetry of the coordination polyhedra around the Nb atoms in metamict euxenite and samarskite resemble those in the crystalline euxenite. Compared with crystalline fergusonite, a decrease in the distortion of the Nb-O octahedra is observed in metamict fergusonite. The structures of the second nearest neighbors (the metal-metal interactions) are largely disrupted in the metamict specimens except for metamict zircon and samarskite with high trivalent iron concentration. Nb in metamict samarskite is in octahedral coordination by oxygen and is similar to that in euxenite.     

Effects of F,B2O3 and P2O5 on the solubility of water in haplogranite melts compared to natural silicate melts

The effects of F, B₂O₃ and P₂O₅ on the H₂O solubility in a haplogranite liquid (36 wt. % SiO₂, 39 wt. % NaAlSi₃O₈, 25 wt. % KAlSi₃O₈) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H₂O solubility increases with increasing F and B content of the melt. The H₂O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H₂O solubility increases from 5.94 to 8.22 wt. % H₂O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H₂O solubility increase of 0.53 mol H₂O/mol F. With addition of 4.35 wt. % B₂O₃, the H₂O solubility increases up to 6.86 wt. % H₂O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H₂O/mol B₂O₃. The results allow to define the individual effects of fluorine and boron on H₂O solubility in haplogranitic melts with compositions close to that of H₂O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H₂O solubility was found to be negligible in natural melt compositions. The concominant increase in H₂O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.