Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite

Two pumpellyites with the general formula W ₈ X ₄ Y ₈ Z ₁₂O_56-n (OH) _n were studied using ⁵⁷Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe²⁺ and two Fe³⁺ doublets for the Mitsu pumpellyite, and one Fe²⁺ and two Fe³⁺ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe²⁺(X):Fe³⁺(X):Fe³⁺(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe²⁺:Fe³⁺-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca₈(Fe _0.88 ²⁺ Mg_0.68Fe _0.77 ³⁺ Al_1.66)_Σ3.99(Al_5.67Fe _2.34 ³⁺ )_Σ8.01Si₁₂O_42.41(OH)_13.59 and Ca₈(Mg_1.24Fe _0.65 ²⁺ Fe _0.46 ³⁺ Al_1.66)_Σ4.01(Al_6.71Fe _1.29 ³⁺ )_Σ8.00Si₁₂O_42.14(OH)_13.86, respectively. Mean Y–O distances and volumes of the YO₆ octahedra increase with increasing mean ionic radii, i.e., the Fe³⁺→Al substitution at the Y site. However, change of the sizes of XO₆ octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO₆ octahedra. Thus, the geometrical change of the YO₆ octahedra with Fe³⁺→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO₆ octahedra by the ionic substitution of Fe³⁺ for Al causes gradual change of the octahedra to more symmetrical and regular forms.     

Correlation of irradiation-induced yellow color with the O<Superscript>−</Superscript> hole center in tourmaline

Tourmaline with the general formula XY₃Z₆(BO₃)₃Si₆O₁₈(OH,O)₃(OH,F) and the trigonal space group R3m (C_3v⁵) is known as a gemstone with great variety of colors. Some color centers are related to transition metal ions, and others to electron or hole traps. In this paper we report on a combined study using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and the optical detection of EPR (ODEPR) on a yellow color center produced by -irradiation in colorless Li-bearing elbaite tourmaline from Brazil. The color center is an O^– hole trap center, which is stabilized within the plane spanned by three Y sites, and is located in the structural channels formed by Si₆O₁₈. We suggest that two of the Y sites are substituted by ²⁷Al and the other by ^6,7Li. During the irradiation process atomic hydrogen H⁰ is also produced, which shows the same thermal stability as the hole center (250 °C). Therefore, we assign H⁰ to be the local charge compensator for the hole trap. From the ODEPR measurements we conclude that the yellow color is caused by the O^– hole center. The large negative isotropic Al superhyperfine interaction of the O^– hole trap center is consistent with a calculation of the transferred hyperfine interactions by exchange polarization supporting the proposed defect model of an O^– at the O₁ sites, whereby the O^– is relaxed into the plane formed by three Y ions.     

Chemical composition of planetary nebulae in the Large and Small Magellanic Clouds

The technique of nebular-gas diagnostics was used to find electronic temperatures T _e , concentrations n _e , relative ion concentrations n(A⁺ⁱ )/n(H⁺), and chemical abundances A/H for planetary nebulae in the Large and Small Magellanic Clouds. This analysis took into account inhomogeneities of the nebular-gas density in the nebulae. We determined the pre-galactic helium abundance Y _p and its rate of enrichment dY/dZ for the envelopes of nine nebulae in the Large Magellanic Cloud. Taken together with the Galaxy’s planetary nebulae and HII regions in blue compact dwarf galaxies, Y _p = 0.248 ± 0.002, dY/dZ = 2.31 ± 0.48 and Y _p = 0.247 ± 0.002, dY/dZ = 3.03 ± 0.56, respectively, when macroinhomogeneities and macro/microinhomogeneities of the gas density in galactic nebulae are taken into account.     

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.     

The crystal chemistry of pumpellyite: An X-ray Rietveld refinement and 57Fe Mössbauer study

Pumpellyite of the general formula W₈X₄Y₈-Z₁₂O_56-n(OH)_n contains Fe, Al and Mg in two crystallographically different octahedral sites. Three different pumpellyite samples covering the known compositional field from Al- to Fe-rich have been studied to determine the valence state and intracrystalline partitioning of the Fe cations between the two independent octahedral sites. Fe⁺² and Fe⁺³ cation partitioning is interpreted on the basis of results obtained by ⁵⁷Fe Mössbauer spectroscopy at 293 and 77 K and from Rietveld structure analysis performed on powder X-ray diffraction data. Pumpellyite from low-grade metamorphic rocks typically contains a majority of iron in the Fe⁺³ oxidation state, which is found in the smaller and less symmetrical octahedral Y-site. Fe⁺² was also present in all pumpellyite samples studied and it is located in the larger and more symmetrical octahedral X-site.     

Enhanced Oxygen Isotope Determination in Uranium Oxides Using BrF5 Fluorination

A new method for accurate determination of oxygen isotopes in uranium oxides encountered in the nuclear fuel cycle was developed using the conventional BrF₅ fluorination technique. Laser‐assisted fluorination was tested for comparison. We focused on fine powders of triuranium octoxide (U₃O₈), uranium dioxide (UO_2±x with 0 ≤ x ≤ 0.25), uranium trioxide (UO₃.nH₂O, with 0.8 ≤ n ≤ 2) and diuranates (M₂U₂O₇.nH₂O, with M = NH₄, Na or Mg_0.5 and 0 ≤ n ≤ 6). Fluorination at room temperature and heating under vacuum at 150 °C are shown to eliminate both adsorbed and structural water from the powder samples. Precision fit for purpose of δ¹⁸O values (± 0.3‰, 1s) and oxygen yields (close to 100%) were obtained for U₃O₈ and UO₂ where oxygen is only bound to uranium. A lower precision was observed for UO₃.nH₂O and M₂U₂O₇.nH₂O where oxygen is both present in the structural H₂O and bonded to uranium and where the extracted O_2(g) can be contaminated by NF₃ and NO_x compounds. Laser‐assisted fluorination gave shifted δ¹⁸O values between +0.8 and +1.4‰ for U₃O₈, around ?0.8‰ for UO₃.nH₂O and between ?3.9 and ?4.5‰ for M₂U₂O₇.nH₂O (± 0.3‰, 1s) compared with the conventional method.     

The crystal structure of an aluminum-rich schorl overgrown by boron-rich olenite from Koralpe, Styria, Austria

Summary The first natural tourmaline (because tourmaline with ^[4]B has also been synthesized, we distinguish here between natural and synthetic tourmaline) that has been unequivocally demonstrated to contain B as a substituent at the T sites was described from Koralpe, Styria, Austria. This colourless B-rich olenite occurs as rims overgrowing schorl (black crystals up to a few cm) that has not yet been structurally characterized. A crystal structure refinement (R = 0.019) of this Al-rich schorl shows that ^[4]B occurs in the overgrown schorl; the optimized occupants of the atomic positions yield ^X (Na_0.64Ca_0.10K_0.06□_0.20) ^Y (Fe²⁺ _1.72Al_1.08Ti_0.11Zn_0.03□_0.06) ^Z (Al_5.70Mg_0.20Fe_0.08 ²⁺Mn_0.02) (^[3]BO₃)_3.00 ^T (Si_5.76 ^[4]B_0.24)O₁₈ [F_0.11(OH)_3.31O_0.58]. This is the first known (Al-rich) schorl where a structure refinement has detected ^[4]B. Comparing the structure refinements and the chemical composition of the Koralpe schorl and other ^[4]B-bearing tourmalines with tourmalines which contain no ^[4]B, it is of interest that only structure refinements of tourmalines which are low in magnesium and with a higher component of olenite show substantial amounts of ^[4]B; the role of Mg in controlling the amount of ^[4]B is not known, but it seems that an Al-component on the Y site (olenite-component), a boron-enriched environment and special P-T-t conditions are necessary to get tourmaline with substantial amounts of ^[4]B. Received July 7, 2000; revised version accepted June 6, 2001     

A CNDO/2 molecular orbital study of the silica polymorphs quartz,cristobalite, and coesite

CNDO/2 MO calculations on H₁₂Si₅O₁₆ clusters modeling silicate tetrahedral linkage in the silica polymorphs show total energy minima at bent SiOSi angles and a correlation between the Si-O bond lengths, d(Si-O), used in the calculation and the minimum energy value of the SiOSi angle. Calculations on hydrogen saturated Si₅O₁₆ clusters isolated from the structures of low quartz, low cristobalite and coesite which were adjusted by DLS methods so that all d(Si-O) equal 1.61 Å and all _L OSiO equal 109.47° yield Mulliken bond overlap populations, n(Si-O), and Si-O two-center energies, E(Si-O), which correlate with observed bond lengths; shorter bonds involve larger n(Si-O) values and more negative E(Si-O) values.

     

Kriging with strings of data

The concept of a random function and, consequently, the application of kriging cells for the implicit assumption that the data locations are embedded within an infinite domain. An implication of this assumption is that, all else being equal, outlying data locations will receive greater weight because they are seen as less redundant, hence, more informative of the infinite domain. A two- step kriging procedure is proposed for correcting this siring effect. The first step is to establish the total kriging weight attributable to each string. The distribution of that total weight to the samples in the string is accomplished by a second stage of kriging. In the second stage, a spatial redundancy measure r_(n) is used in place of the covariance measure in the data-data kriging matrix. This measure is constructed such that each datum has the same redundancy with the (n)data of the string to which it belongs. This paper documents the problem of kriging with strings of data, develops the redundancy measure r_(n),and presents a number of examples.     

Fivegite K4Ca2[AlSi7O17(O2 ? xOHx)][(H2O)2 ? xOH]Cl: A new mineral species from the Khibiny alkaline pluton of the Kola Peninsula in Russia

A new mineral fivegite has been identified in a high-potassium hyperalkaline pegmatite at Mt. Rasvumchorr in the Khibiny alkaline complex of the Kola Peninsula in Russia. This mineral is a product of the hydrothermal alteration of delhayelite (homoaxial pseudomorphs after its crystals up to 2 × 3 × 10 cm in size). Hydrodelhayelite, pectolite, and kalborsite are products of fivegite alteration. The associated minerals are aegirine, potassic feldspar, nepheline, sodalite, magnesiumastrophyllite, lamprophyllite, lomonosovite, shcherbakovite, natisite, lovozerite, tisinalite, ershovite, megacyclite, shlykovite, cryptophyllite, etc. Areas of pure unaltered fivegite are up to 2 mm in width. The mineral is transparent and colorless; its luster is vitreous to pearly. Its Cleavage is perfect (100) and distinct (010). Its Mohs hardness is 4, D(meas) = 2.42(2), and D(calc) = 2.449 g/cm³. Fivegite is optically biaxial positive: α 1.540(1), β 1.542(2), γ 1.544(2), and 2V(meas) 60(10)°. Its orientation is X = a, y = c, and Z = b. Its IR spectrum is given. Its chemical composition (wt %; electron microprobe, H₂O determined by selective sorption) is as follows: 1.44 Na₂O, 19.56 K₂O, 14.01 CaO, 0.13 SrO, 0.03 MnO, 0.14 Fe₂O₃, 6.12 Al₂O₃, 50.68 SiO₂, 0.15 SO₃, 0.14 F, 3.52 Cl, 4.59 H₂O; −O = −0.85(Cl,F)2; total 99.66. The empirical formula based on (Si + Al + Fe) = 8 is H_4.22K_3.44Na_0.39Ca_2.07Sr_0.01Fe_0.01Al_1.00Si_6.99O_21.15F_0.06Cl_0.82(SO₄)_0.02. The simplified formula is K₄Ca₂[AlSi₇O₁₇(O_{2 − x} OH _x ][(H₂O)_{2 − x} OH _x ]Cl (X = 0−2). Fivegite is orthorhombic: Pm2₁ n, a = 24.335(2), b = 7.0375(5), c = 6.5400(6) ?, V = 1120.0(2) ?³, and Z = 2. The strongest reflections of the X-ray powder pattern are as follows (d, ?, (I, %), [hkl]): 3.517(38) [020], 3.239(28) [102], 3.072(100) [121, 701], 3.040(46) [420, 800, 302], 2.943 (47) [112], 2.983(53) [121], 2.880 (24) [212, 402], 1.759(30) [040, 12.2.0]. The crystal structure was studied using a single crystal: R _hkl = 0.0585. The base of fivegite structure is delhayelite-like two-layer terahedral blocks [(Al,Si)₄Si₁₂O₃₄(O_{4 − x} OH _x )] linked by Ca octahedral chains. K⁺ and Cl⁻ are localized in zeolite-like channels within the terahedral blocks, whereas H₂O and OH occur between the blocks. The mineral is named in memory of the Russian geological and mining engineer Mikhail Pavlovich Fiveg (1899–1986), the pioneering explorer of the Khibiny apatite deposits. The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences in Moscow. The series of transformations is discussed: delhayelite K₄Na₂Ca₂[AlSi₇O₁₉]F₂Cl—fivegite K₄Ca₂[AlSi₇O₁₇(O_{2 − x} OH _x ]Cl—hydrodelhayelite KCa₂[AlSi₇O₁₇(OH)₂](H₂O)_{6 − x} .     

Crystal chemistry of selenates with mineral-like structures. VI. Hydrogen bonds in the crystal structure of [(H5O2)(H3O)(H2O)][(UO2)(SeO4)2]

The crystal structure of a new compound, [(H₅O₂)(H₃O)(H₂O)][(UO₂)(SeO₄)₂] (monoclinic, P2₁/n a = 8.3105(15), b = 11.0799(14), c = 13.227(2) Å, β = 103.880(13)°, V = 1182.4(3) ų), has been solved by direct methods and refined to R ₁ = 0.036. The structure is based on [(UO₂)(SeO₄)₂]^2? sheet complexes formed by corner-shared UO₇ pentagonal bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the ( $ \bar 1 The crystal structure of a new compound, [(H₅O₂)(H₃O)(H₂O)][(UO₂)(SeO₄)₂] (monoclinic, P2₁/n a = 8.3105(15), b = 11.0799(14), c = 13.227(2) ?, β = 103.880(13)°, V = 1182.4(3) ?³), has been solved by direct methods and refined to R ₁ = 0.036. The structure is based on [(UO₂)(SeO₄)₂]²⁻ sheet complexes formed by corner-shared UO₇ pentagonal bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (01) plane. Oxonium ions and water molecules forming [(H₃O)·(H₂O)·(H₅O₂)]²⁺ complexes are interlayer. Among minerals, the existence of (H₅O₂)⁺ has been unambiguously confirmed only in rhomboclase, (H₅O₂)⁺[Fe₂(SO₄)₂(H₂O)₂]. Original Russian Text ? S.V. Krivovichev, 2008, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2008, No. 2, pp. 123–130.     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

Remineralization Ratios in the Subtropical North Pacific Gyre

Based on a new mixing model of two end-members, the water column remineralization ratios of P/N/C_org - O₂ = 1/13 ± 1/135 ± 18/170 ± 9 are obtained for the Hawaii Ocean Time-series (HOT) data set at station ALOHA. The traditional Redfield ratios of P/N/C_org/–O₂ = 1/16/106/138 have standard deviations of more than 50%, when they are based on the average composition of phytoplankton. Apparently, the remineralization processes in the water column have smoothed out the observed large variability of plankton compositions. A new molar formula for the remineralized plankton may be written as ₁₃₅H₂₈₀O₁₀₅N₁₃P or C₂₅(CH₂O)₁₀₁(CH₄)₉(NH₃)₁₃(H₃PO₄). Oxidation of this formula results inC₂₅(CH₂O)₁₀₁(CH₄)₉(NH₃)₁₃(H₃PO₄) + 170O₂ 135CO₂ + 132H₂O + 13NO₃ ^- + H₂PO₄ ^- + 14H⁺.For comparison, remineralization using Redfield's formula gives:(CH₂O)₁₀₆(NH₃)₁₆(H₃PO₄) + 138O₂ 106CO₂ + 122H₂O + 16NO₃ ^-+ H₂PO₄ ^- + 17H⁺     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996     

Low-temperature thermodynamic properties of disordered zeolites of the natrolite group

 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na_1.90K_0.22Ca_0.06)[Al_2.24Si_2.76O₁₀]·nH₂O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K⁻¹ mol⁻¹ for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K⁻¹ mol⁻¹ for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C _p (298.15)=359.1 J K⁻¹ mol⁻¹, S(298.15) −S(0)=362.8 J K⁻¹ mol⁻¹. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001     

Correlations between 29Si, 17O and 1H NMR properties and local structures in silicates: an ab initio calculation

In order to gain insight into the correlations between ²⁹Si, ¹⁷O and ¹H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)₄ monomers (isolated as well as interacting), Si₂O(OH)₆ dimers (C₂ symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si₃O₂(OH)₈ linear trimers (C₂ symmetry) with varying Si-O-Si angles, Si₃O₃(OH)₆ three-membered rings (D₃ and C₁ symmetries), Si₄O₄(OH)₈ four-membered ring (C₄ symmetry) and Si₈O₁₂(OH)₈ octamer (D₄ symmetry). The calculated ²⁹Si, ¹⁷O and ¹H isotropic chemical shifts (δ_i ^Si, δ_i ^O and δ_i ^H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated ¹⁷O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated ¹⁷O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δ_i ^Si and the mean Si-O-Si angle for both Q ¹ and Q ², where Q ⁿ denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ _i ^O and the ¹⁷O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the ¹⁷O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable ¹⁷O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the ¹⁷O QCC and the ²H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ _i ^H increase with the same parameter. Received: 18 July 1997 / Revised, accepted: 23 February 1998     

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H₂O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity–basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy density-of-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for ^[6]Mg _m ^[4] Si _n O_(m+2n) and MgSO₄(H₂O) _n .     

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe₂O₃) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH)₆ polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe₂(OH)₂(H₂O)₈Cu(OH)₄and Fe₃(OH)₄(H₂O)₁₀Cu₂(OH)₆ clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO₄H_n)ⁿ⁻⁶ and Fe(O,OH)₆ polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH)₂. Having identified the bidentate (FeOH)₂Cu(OH)₂⁰ and tridentate (Fe₃O(OH)₂)Cu₂(OH)₃⁰ surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions

     

On the optically biaxial character and heterogeneity of anthracites

The results of the study of optical properties of 13 anthracites from different parts of the world are presented in this paper. Measurements of reflectance values were made on non-oriented vitrinite grains for a minimum of 300 points per sample. The reconstruction of Reflectance Indicating Surfaces (RIS) were made by Kilby's method [Kilby, W.E., 1988. Recognition of vitrinite with non-uniaxial negative reflectance characteristics. Int. J. Coal Geol. 9, 267–285; Kilby, W.E., 1991. Vitrinite reflectance measurement — some technique enhancements and relationships. Int. J. Coal Geol. 19, 201–218]. It was found that the use of Kilby's method for strongly anisotropic materials like anthracites did not give unambiguous results. Some improvement in Kilby's method, consisting of the division of the cumulative cross-plot into several elemental components, is suggested. Each elemental cross-plot corresponds to a textural class of anthracite, which is characterized by the values of RIS main axes R_MAX^(k), R_INT^(k) and R_MIN^(k) (k=1,2,…n; n — number of classes). The global texture of anthracite is characterized as a RIS with main axes calculated as the weighted means of , and for each class of this anthracite.The division of cumulative Kilby's cross-plot on elemental components makes possible the calculation of new coefficients H_t and H₁₀ characterizing the heterogeneity of the structure and texture of anthracites. The results of our study show that all anthracites have biaxial negative textures, but their heterogeneity varies in a wide range of H_t and H₁₀ coefficients depending upon the individual coal basin.