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1.
The mineral ussingite, Na2AlSi3O8(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm–1, and a possible OH librational bending mode at 1295 cm–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the 1H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and 1H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and 1H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.  相似文献   

2.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

3.
The Karacadağ (Kulu-Konya) area is one of the main volcanic provinces in Central Anatolia. The Karacadağ volcanites are composed of large volumes of andesitic-dacitic lavas associated with pyroclastics and small volumes of alkali basalt, trachybasalt and trachyandesite lavas. Two groups of volcanic rocks can be distinguished: (1) calcalkaline rocks including andesites and dacites, and (2) alkaline rocks including basalts, trachybasalts and trachyandesites. 40Ar/39Ar ages show that the Karacadağ volcanites were erupted during Early Miocene (ca.18–19 Ma) and suggest that alkaline volcanites succeed shortly afterwards calcalkaline volcanites. Major oxides and trace elements plotted versus SiO2 suggest fractionation of hornblende, Fe–Ti oxide and apatite for calcalkaline volcanic rocks and olivine, clinopyroxene and Fe–Ti oxide for alkaline volcanic rocks in the magmatic evolution. The incompatible trace element patterns of the calcalkaline volcanites show enrichment of LILEs (Sr, K, Rb, Ba and Th) and negative HFSEs (Nb, Ta) anomalies suggesting an enriched lithospheric source by a subduction-related process. On the other hand, alkaline volcanites show enrichment of both LILEs and HFSEs suggesting an enriched lithospheric source by small volume melts from the asthenosphere. The rocks also have moderately fractionated REE patterns with (La/Lu)N ratios of 7–24 for calcalkaline and 6–17 for alkaline volcanites. Moreover, the volcanites have relatively low 87Sr/86Sr(t) ratios for between 0.703782 and 0.705129, and high εNd(t) values between +2.25 and +4.49. Generally, the Sr–Nd isotopic compositions of the rocks range from the mantle array to bulk earth. All of these observations and findings suggest that the calcalkaline volcanites were formed in a subduction modified orogenic setting, and the alkaline volcanites in a within-plate setting.  相似文献   

4.
Comparison of polarized optical absorption spectra of natural Ca-rich diopsides and synthetic NaCrSi2O6 and LiCrSi2O6 clinopyroxenes, evidences as vivid similarities, as noticeable differences. The similarities reflect the fact that in all cases Cr3+ enters the small octahedral M1-site of the clinopyroxene structure. The differences are due to some iron content in the natural samples causing broad intense near infrared bands of electronic spin-allowed dd transitions of Fe2+(M1, M2) and intervalence Fe2+/Fe3+ charge-transfer transition, and by different symmetry and different local crystal fields strength of Cr3+ in the crystal structures. The positions of the spin-allowed bands of Cr3+, especially of the low energy one caused by the electronic 4 A 2g → 2 T 1g transition, are found to be in accordance with mean M1–O distances. The local relaxation parameter ε calculated for limCr 3+ → 0 from the spectra and interatomic á Cr - O ñ \left\langle {Cr - O} \right\rangle and á Mg - O ñ \left\langle {Mg - O} \right\rangle distances yields a very high value, 0.96, indicating that in the clinopyroxene structure the local lattice relaxation around the “guest” ion, Cr3+, deviates greatly from the “diffraction” value, ε = 0, than in any other known Cr3+-bearing systems studied so far. Under pressure the spin-allowed bands of Cr3+ shift to higher energies and decrease in intensity quite in accordance with the crystal field theoretical expectations, while the spin-forbidden absorption lines remain practically unshifted, but also undergo a strong weakening. There is no evident dependence of the Racah parameter B of Cr3+ reflecting the covalence of the oxygen-chromium bond under pressure: within the uncertainty of determination it may be regarded as practically constant. The values of CrO6 octahedral modulus, k\textpoly\textloc k_{\text{poly}}^{\text{loc}} , derived from high-pressure spectra of natural chromium diopside and synthetic NaCrSi2O6 kosmochlor are very close, ~203 and ~196 GPa, respectively, being, however, nearly twice higher than that of MgO6 octahedron in diopside, 105(4) GPa, obtained by Thompson and Downs (2008). Such a strong stiffening of the structural octahedron, i.e. twice higher value of k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} comparing with that of k\textMg2 + \textloc k_{{{\text{Mg}}^{2 + } }}^{\text{loc}} , may be caused by simultaneous substitution of Ca2+ by larger Na+ in the neighboring M2 sites at so-called jadeite-coupled substitution Mg2+ + Ca2+ → Cr3+ + Na+. It is also remarkable that the values of CrO6 octahedral modulus of NaCrSi2O6 kosmochlor obtained here are nearly twice larger than that of 90(16) GPa, evaluated by high-pressure X-ray structural refinement by Origlieri et al. (2003). Taking into account that the overall compressibility of the clinopyroxene structure should mainly be due to the compressibility of M1- and M2-sites, our k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} -value, ~196 GPa, looks much more consistent with the bulk modulus value, 134(1) GPa.  相似文献   

5.
KAlSi3O8 sanidine dissociates into a mixture of K2Si4O9 wadeite, Al2SiO5 kyanite and SiO2 coesite, which further recombine into KAlSi3O8 hollandite with increasing pressure. Enthalpies of KAlSi3O8 sanidine and hollandite, K2Si4O9 wadeite and Al2SiO5 kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi3O8 hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi3O8 hollandite above 298 K as Cp=3.896 × 102–1.823 × 103T–0.5–1.293 × 107T–2+1.631 × 109T–3 (Cp in J mol–1 K–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO4 kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi3O8 determined in this study put some constraints on the stability range of KAlSi3O8 hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.  相似文献   

6.
Orthorhombic amphiboles with excess OH, which can be schematically deduced from anthophyllite by the combined substitutions Mg2+ + O2–Li++OH– and Mg2+2 Li+, were synthesized at 750–875° C/1 kbar in the system Li2O-MgO-SiO2-H2O. Their phase relations are presented for 800° C/1 kbar . An amphibole with the analytical composition 2.70 wt% Li2O, 31.1 wt% MgO, 63.0 wt% SiO2, and 3.29 wt% H2O has lattice constants a 0 18.588 (11), b 0 17.966 (10), c 0 5.262 (3) Å, V 0 1,757.2 (1.5) Å3 (referred to Space Group Pnma). The OH-valence vibrational spectrum of this amphibole showed v OH bands at 3,667, 3,708, and 3,725 (shoulder) cm–1, which are ascribed to OH in the configurations (MgMgMg)-OH, (MgMgMg)-OH-Li (Li in the A-site) of the pseudotrigonal (M1M1M3)-OH arrangement in the amphibole structure, and to Si-OH, respectively. No explanation can at present be offered for an additional shoulder at 3,695 cm–1. The proposed structural formula is (Li0.27 0.73)(Li1.11 Mg0.89)· (Mg5)(Si8.01O21.20(OH)0.80)(OH)2.00.  相似文献   

7.
Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering, confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith the peak position (quartz ε = 89,000 ± 15,000  \textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000  \textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000  \textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling the Earth’s deep water cycle.  相似文献   

8.
The synthetic LiGaSi2O6 clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi2O6), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si2O6 group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

9.
Summary The crystal structure of hendricksite, a trioctahedral mica of biotite type, characterized by high Zn2+ and Mn2+ contents has been refined by least square methods. The structural formula is: (K0.89Na0.10Ba0.04)(Mg1.57Zn0.54Mn 0.40 2+ Fe 0.25 2+ Al0.07Ti0.07Cr0.01)(Si2.92Al1.08)O10 (OH)2. The space group isC2/m and the cell parameters are:a=5.340(2) Å,b=9.524(2) Å,c=10.235(3) Å, =100.07(2)o, the cell volume isV=497.98 Å3. The final unweightedR=0.072. Average cation-anion distances in polyhedra are: T–O=1.659 Å, M(1)–O=2.093 Å, M(2)–O=2.088 Å, A–Olong=3.316 Å and A–Oshort=3.004 Å; A is the alkaline cation. The rotation angle of tetrahedra is =6.7°. The analysis of electron densities, of the dimensions and distorsions of polyhedra shows that Zn2+ is exclusively in octahedral sites; there is no order between six-fold coordinated cations. A comparison between the structural features of hendricksite and those of the two main end-members of biotites, phlogopite and annite, is presented.The effect of the strong covalence of Zn–O bonds is particularly visible on the dimensions and orientations of the thermal ellipsoids of octahedral sites M(1) and M(2) which contain zinc. In all the published structures of trioctahedral micas, the ellipsoids of cationic sites are uniaxial positive, elongated parallel toc *. In hendricksite, this is observed only for the two zinc-free sites (T and A; in the octahedra M(1) and M(2), which contain zinc, the ellipsoids are approximately uniaxial negative, flattened parallel toa, which is a unique situation.Zinc which habitually favours the tetrahedral coordinations with oxygen, enters the octahedra only, i.e. the chemically anisotropic sites, in hendricksite. The strong polarizability of Zn2+ is proposed to explain this behaviour.An examination of the behaviour of Zn2+ in other compounds shows that this situation is general, zinc favours chemically anisotropic sites and specially those adjacent to OH or H2O.
Affinement de la structure cristalline de la hendricksite, mica trioctaédrique potassique riche en Zn et Mn; une contribution à la connaissance cristallochimique des minéraux zincifères
Résumé On a affiné par moindres carrés la structure de la hendricksite, mica trioctaédrique de type biotite, caractérisé par une teneur élevée en Zn2+ et Mn2+. La formule structurale de ce mica est: (K0m89Na0,10Ba0,04)(Mg1,57Zn0,54Mn 0,40 2+ Fe 0,25 2+ Al0,07Ti0,07Cr0,01)(Si2,92Al1,08)O10(OH)2. Le groupe spatial estC2/m et les paramètres de la maille:a=5,340(2) Å,b=9,254(2) Å,c=10,235(3) Å, =100,07(2)°; le volume de la maille estV=497,98 Å3. Le résidu final non-pondéré estR=0,072. Les distances cation-anion moyennes dans les polyèdres sont les suivantes: T–O=1,659 Å, M(1)–O=2,093 Å, M(2)–O=2,088 Å, A–Olong=3,316 Å et A–Ocourt=3,004 Å où A désigne le cation alcalin. L'angle de rotation tétraédrique, =6,7°, est très semblable à celui de la phlogopite. L'analyse des densités électroniques, des dimensions et distorsions des polyèdres montre que Zn2+ est exclusivement en coordinance octaédrique et qu'il n'y a pas d'ordre entre les cations hexacoordonnés. On présente une comparaison des caractères structuraux de la hendricksite avec ceux des deux principaux pôles des biotites, la phlogopite et l'annite.L'effet de la forte covalence de la liaison Zn–O est particulièrement visible sur les dimensions et orientations des ellipsoides d'agitation thermique des deux sites octaédriques, sites zincifères. Dans toutes les structures de micas trioctaédriques publiées, les ellipsoides des sites cationiques sont uniaxes positifs, allongés parallèlement àc *, ce qui s' observe effectivement dans les deux sites non-zincifères (T et A) de la hendricksite, par contre, dans les octaèdres M(1) et M(2), qui contiennent le zinc, les ellipsoides sont approximativement uniaxes négatifs, applatis parallèlement àa, ce qui est une situation unique.Le zinc, qui se fixe généralement en sites tétraédriques dans les structures de type oxyde, occupe les sites octaédriques, c'est-à-dire les sites chimiquement anisotropes dans la hendricksite. La forte polarisabilité de Zn2+ est proposée pour expliquer ce comportement.Un examen du comportement de Zn2+ dans d'autres phases montre que cette situation est tout à fait générale, le zinc privilégiant les sites chimiquement anisotropes et en particulier ceux adjacents à OH où H2O.
  相似文献   

10.
There are large areas of Permian basaltic rocks in the Tarim basin (PBRT) in northwestern China. Precise Ar–Ar dating of these rocks revealed an eruption age span of 262 to 285 Ma. Most of the PBRT is composed of alkaline basaltic rocks with high TiO2 (2.43%–4.59%, weight percent), high Fe2O3 + FeO (12.63%–17.83%) and P2O5 (0.32%–1.38%) contents. Trace elements of these rocks have affinities with oceanic island basalts (OIB), as shown in chondrite normalized rare earth elements (REE) diagrams and primitive mantle normalized incompatible elements diagrams. The rocks show complex Sr–Nd isotopic character based on which they can be subdivided into two distinct groups: group 1 has relatively small initial (t = 280 Ma)87Sr/86Sr ratio ( 0.7048) and positive εNd(t) (3.42–4.66) values. Group 2 has relatively large initial 87Sr/86Sr ratio (0.7060–0.7083) and negative εNd(t) (from − 2.79 to − 2.16) values. Lead isotopes are even more complex with variations of (206Pb/204Pb)t, (207Pb/204Pb)t and (208Pb/204Pb)t ranging from 17.9265 to 18.5778, 15.4789 to 15.6067 and 37.2922 to 38.1437, respectively. Moreover, these two groups have different trace elements ratios such as Nb/La, Ba/Nb, Zr/Nb, Nb/Ta and Zr/Hf, implying different magmatic processes. Based on the geochemistry of basaltic rocks and an evaluation of the tectonics, deformation, and the compositions of crust and lithospheric mantle in Tarim, we conclude that these basaltic rocks resulted from plume–lithosphere interaction. Permian mantle plume caused an upwelling of the Tarim lithosphere leading to melting of the asthenospheric mantle by decompression. The magma ascended rapidly to the base of lower crust, where different degrees of assimilation of OIB-like materials and fractionation occurred. Group 1 rocks formed where the upwelling is most pronounced and the assimilation was negligible. In other places, different degrees of assimilation and fractionation account for the geochemical traits of group 2.  相似文献   

11.
The investigation of the NH3 loss in the NH4+-vermiculite (Santa Olalla) by thermogravimetry, evolved gas analysis, chemical analysis, X-ray diffraction and IR spectroscopy is reported here. The mass loss during heating takes place in two steps at about 650 and 825 °C. Additionally, the releases of H2O and NH3 occurs simultaneously. The experimental results indicate that the protons remaining in the interlayer space after NH3 removal trigger the H2O release. X-ray diffraction shows that during the decomposition of NH4+-vermiculite there are two domains with different interlayer spaces at ~9 and ~10 Å. As the decomposition proceeds, the intensity of the 9 Å peak increases at the expense of the second one. The change in the IR-stretching modes of the structural OH groups during heating indicates that the OH groups surrounded by 3Mg2+ or 2Mg2+Fe2+ are released at lower temperatures than those with environments like 2Mg2+Fe3+, 2Mg2+Al3+ or more complex ones.  相似文献   

12.
The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4–H1... O1, O4–H2... O2, O4–H3... O3 and O4–H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton–proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4–H3... O3 and O4–H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4–H1... O1 and O4–H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm–1 was assigned to the OH-stretching of the O4–H3... O3 bond, while the band at 3600 cm–1 was attributed to OH-stretching of the O4–H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100–150 cm–1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4–H3... O3 and O4–H4... O4 bonds at 670 K occur at a rate of about 1.96 THz.  相似文献   

13.
Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe2O3 by wet chemistry, and for H2O by manometric measurement as H2. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe3+/(Fe2++Fe3+) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe2+. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe2O3, and H2O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca2Mg5Si8 O22(OH)2(a Trem) in hornblende for use in equilibria that constrain the activity of H2O (a H 2O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a Trem (usually<0.01), consequetly yielding extremely low a H 2O. If an oxy-amphibole component is present, the calculated a Trem and H2O is further reduced. An oxy-amphibole component of 25% reduces the calculated H2O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X OH in the hydroxyl site (i.e., X OH=1, or X OH=1–X Cl–X f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H2O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe2O3 and H2O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan  相似文献   

14.
A novel complex continuous system of solid solutions involving vauquelinite Pb2Cu(CrO4)(PO4)(OH), bushmakinite Pb2Al(VO4)(PO4)(OH), ferribushmakinite Pb2Fe3+(VO4)(PO4)(OH), and a phase with the endmember formula Pb2Cu(VO4)(PO4)(H2O) or Pb2Cu(VO4)(РО3ОН)(ОН) is studied based on samples from the oxidation zone of the Berezovskoe, Trebiat, and Pervomaisko-Zverevsky deposits in the Urals, Russia. This is the first natural system in which chromate and vanadate anions show a wide range of substitutions and the most extensive solid solution system involving (CrO4)2– found in nature. The major couple substitution is Cr6+ + Cu2+ ? V5+ + M3+, where M = Fe, Al. The correlation coefficients calculated from 125 point analyses are: 0.96 between V and (Fe + Al), 0.96 between Cr and (Cu + Zn),–0.96 between V and (Cu + Zn),–0.97 between Cr and (Fe + Al), and–0.97 between (Fe + Al) and (Cu + Zn). The substitutions V5+ ? Cr6+ (correlation coefficient–0.98) and to a lesser extent P5+ ? As5+ (correlation coefficient–0.86) occur at two types of tetrahedral sites, whereas the metal–nonmetal/metalloid substitutions, i.e., V or Cr for P or As, are minor. The substitution Fe3+ ? Al3+ is also negligible in this solid solution system.  相似文献   

15.
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 (δi Si, δi O and δi 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 δi 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  相似文献   

16.
The local and geometrical structure around gold (III) e.g., Au3+ ions in aqueous solution with different OH−/Cl− molar ratios, has been investigated by X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure (XANES) spectra of [AuCln(OH)4−n]− solutions have been calculated and the multiple-scattering spectral features have been attributed to Cl d-states, axial water molecules and the replacement of Cl− ligands by OH− ligands. A square–planar geometry for [AuCln(OH)4−n]− with two axial water molecules has been identified. Moreover, a spectral correlation between XANES features and the type of planar atoms has been identified. By extended X-ray absorption fine structure spectra (EXAFS), the planar Au bond distances in the solutions have also been determined, e.g., 2.28 Å for Au–Cl and 1.98 Å for Au–O, respectively. The same EXAFS analysis provides evidence that the peak at about 4.0 Å in solutions with the lowest OH−/Cl− molar ratio arises from collinear Cl–Au–Cl multiple-scattering contributions. For the first time, a complete detailed reconstruction of the hydration structure of an Au ion at different pH values has been achieved.  相似文献   

17.
Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and 87Sr/86Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE2O3, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The 87Sr/86Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ18O + 3 to + 5‰VSMOW and δ13C ? 3.5 to ? 3.2‰VPDB). In contrast, dolomite in the same samples has similar δ13C values but much higher δ18O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ18O and 87Sr/86Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ18O + 7.7 to + 10.3‰ and δ13C ?5.2 to ?6.0‰; 87Sr/86Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.  相似文献   

18.
The nature of the petrogenetic links between carbonatites and associated silicate rocks is still under discussion (i.e., [Gittins J., Harmer R.E., 2003. Myth and reality of the carbonatite–silicate rock “association”. Period di Mineral. 72, 19–26.]). In the Paleozoic Kola alkaline province (NW Russia), the carbonatites are spatially and temporally associated to ultramafic cumulates (clinopyroxenite, wehrlite and dunite) and alkaline silicate rocks of the ijolite–melteigite series [(Kogarko, 1987), (Kogarko et al., 1995), (Verhulst et al., 2000), (Dunworth and Bell, 2001) and (Woolley, 2003)]. In the small (≈ 20 km2) Vuoriyarvi massif, apatite is typically a liquidus phase during the magmatic evolution and so it can be used to test genetic relationships. Trace elements contents have been obtained for both whole rocks and apatite (by LA-ICP-MS). The apatites define a single continuous chemical evolution marked by an increase in REE and Na (belovite-type of substitution, i.e., 2Ca2+ = Na+ + REE3+). This evolution possibly reflects a fractional crystallisation process of a single batch of isotopically homogeneous, mantle-derived magma.The distribution of REE between apatite and their host carbonatite have been estimated from the apatite composition of a carbonatite vein, belonging to the Neskevara conical-ring-like vein system. This carbonatite vein is tentatively interpreted as a melt. So, the calculated distribution coefficients are close to partition coefficients. Rare earth elements are compatible in apatite (D > 1) with a higher compatibility for the middle REE (DSm : 6.1) than for the light (DLa : 4.1) and the heavy (DYb : 1) REE.  相似文献   

19.
A natural datolite CaBSiO4(OH) (Bergen Hill, NJ, USA), before and after gamma-ray irradiation (up to ~70 kGy), has been investigated by single-crystal and powder electron paramagnetic resonance (EPR) spectroscopy from 10 to 295 K. EPR spectra of gamma-ray-irradiated datolite show the presence of a boron-associated oxygen hole center (BOHC) and an atomic hydrogen center (H0), both of which grow with increasing radiation dose. The principal g and A(11B) values of the BOHC at 10 K are: g 1 = 2.04817(3), g 2 = 2.01179(2), g 3 = 2.00310(2), A 1 = −0.401(7) mT, A 2 = −0.906(2) mT, A 3 = −0.985(2) mT, with the orientations of the g 1 and A 1 axes approximately along the B–OH bond direction. These experimental results suggest that the BOHC represents hole trapping on the hydroxyl oxygen atom after the removal of the proton (i.e. a [BO4]0 center): via a reaction O3BOH → O3BO· + H0, where · denotes the unpaired electron. Density functional theory (DFT) calculations (CRYSTAL06, B3PW, all-electron basis sets, and 1 × 2 × 2 supercell) support the proposed structural model and yield the following 11B hyperfine coupling constants: A 1 = −0.429 mT, A 2 = −0.901 mT, A 3 = −0.954 mT, in excellent agreement with the experimental results. The [BO4]0 center undergoes the onset of thermal decay at ~200°C and is completely annealed out at 375°C but can be restored readily by gamma-ray irradiation. Isothermal annealing experiments show that the [BO4]0 center exhibits a second-order thermal decay with an activation energy of 0.96 eV. The confirmation of the [BO4]0 center (and its formation from the O3BOH precursor) in datolite has implications for not only understanding of BOHCs in alkali borosilicate glasses but also their applications to nuclear waste disposal.  相似文献   

20.
 The magnetic behavior of the Jahn-Teller structure braunite, (Mn2+ 1−yM y )(Mn3+ 6− x Mx)SiO12, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe3+ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001  相似文献   

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