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1.
In a group of minerals of reasonable complexity in which the structure topology is related but not identical, the general relation between structure topology and chemical composition is not known. This problem is of major significance. The structural hierarchy and stereochemistry are described for 27 titanium disilicate minerals that contain the TS (titanium-silicate) block, a central trioctahedral (O) sheet and two adjacent (H) sheets of [5]- and [6]-coordinated polyhedra and (Si2O7) groups and related delindeite. The TS block is characterized by a planar cell based on translation vectors, t 1 and t 2 , with t 1 ～ 5.5 and t 2 ～ 7 Å and t 1 ∧ t 2 close to 90°. The general formula of the TS block is A 2 P B 2 P M 2 H M 4 O (Si 2 O 7 ) 2 X 4 + n, where M 2 H and M 4 O = cations of the H and O sheets; MH = Ti (= Ti + Nb), Zr, Mn2+, Ca; MO = Ti, Zr, Mn2+, Ca, Na; A P and B P are cations at the peripheral (P) sites = Na, Ca, Ba; X = anions = O, OH, F; n = 0, 2, 4; the core part of the TS block is shown in bold and is invariant. Cations in each sheet of the TS block form a close-packed layer and the three layers are cubic close packed.There are three topologically distinct TS blocks, depending on the type of linkage of two H sheets and the central O sheet. The H sheets of one TS block attach to the O sheet in the same manner. All structures consist of a TS block and an I (intermediate) block that comprises atoms between two TS blocks. Usually, the I block consists of alkali and alkaline-earth cations, (H2O) groups and oxyanions (PO4)3?, (SO4)2? and (CO3)2?. These structures naturally fall into four groups, based on differences in topology and stereochemistry of the TS block. In Group I, Ti = 1 apfu Ti occurs in the O sheet, and (Si2O7) groups link to a Na polyhedron of the O sheet (linkage 1). In Group II, Ti = 2 apfu, Ti occurs in the H sheet, and (Si2O7) groups link to two M 2+ octahedra of the O sheet adjacent along t 2 (linkage 2). In Group III, Ti = 3 apfu, Ti occurs in the O and H sheets, and (Si2O7) groups link to the Ti octahedron of the O sheet (linkage 1). In Group IV, Ti = 4 apfu (the maximum possible content of Ti in the TS block), Ti occurs in the O and H sheets, and (Si2O7) groups link to two Ti octahedra of the O sheet adjacent along t 1 (linkage 3). The stability of the TS block is due to the ability of Ti (Nb) to have an extremely wide range in Ti (Nb)-anion bond lengths, 1.68–2.30 Å, which allows the chemical composition of the TS block to vary widely. In crystal structures so far known, only one type of TS block occurs in a structure. The TS block propagates close-packing of cations onto the I block. The general structural principles and the relation between structure topology and chemical composition are described for the TS-block minerals. These principles allow prediction of structural arrangements and possible chemical compositions, and testing whether or not all aspects of the structure and chemical formula of a mineral are correct. Here, I show how these principles work, and review recent results that show the effectiveness of these principles as a predictive technique.  相似文献   

2.
The field of mechanical energy transfer from the atmosphere to the ocean is computed for the first time. The numerical simulation of waves within the Indian Ocean (IO) water area for the period of 1998?C2009 is used. Mechanical energy transfer is described by two integrated parameters calculated per area unit: the speed of complete energy flux from wind to waves, I E (x, t), and the speed of complete losses in the energy of wind waves, D E (x, t). In order to solve this problem, the wind field W(x, t) (the NCEP/NOAA data) is used; the I E (x, t) and D E (x, t) fields are calculated on the basis of the WAM numerical model containing a modified source function. The results obtained allow us, first, to assess the characteristic spatial distribution of zones ??pumped?? by the wind with mechanical energy for both the wave field and the upper layer of the ocean by seasons, years, and the whole period discussed, second, to determine the extreme and average zonal values of I E (x, t) and D E (x, t), the degree of their shift spacing and balance B E = (I E + D E ); and third, to define the characteristic time scales of variations in the wind field and wave field energies, caused by energy transfer from the wind to waves in the zones and within the Indian ocean as a whole. These results significantly specify the climatic estimates obtained earlier.  相似文献   

3.
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4.
Two new protoamphibole-type amphiboles with space group type Pnmn, have been found in nature: protoferro-anthophyllite (Fe0.80Mn0.20)2 (Fe0.98Mg0.02)5 (Si4O11)2(OH)2, and protomangano-ferro-anthophyllite, (Mn0.70Fe0.30)2 (Fe0.82Mg0.18)5 (Si4O11)2(OH)2. Protoferro-anthophyllite (PFA) occurs in pegmatites at both Gifu Prefecture, Japan and at Cheyenne Mountain, El Paso County, Colorado, USA. Protomangano-ferro-anthophyllite, (PMFA) occurs in pegmatites at Fukushima Prefecture and in a Mn mine at Tochigi Prefecture, Japan. Structure determinations of the two amphiboles show that both are isostructural with the synthetic fluorian-amphibole, protoamphibole (= protofluorian-lithian-anthophyllite). A calculation of the procrystal electron density distributions, the bond paths and the bond critical point properties of PFA, PMFA, grunerite and protoamphibole indicates that the M4 cation in these amphiboles is 4-coordinated. A calculation of the electron density distributions at the Becke3LYP/6-311G(2d,p) level for model silicate tetrahedra for these amphiboles and anthophyllite reveals that the value of the electron density at the bond critical points, ρ(r c ), for the SiO(nbr) bonds is larger, on average (0.93 e/Å3), than that for the SiO(br) bonds (0.90 e/Å3). The observed SiO bond lengths decrease linearly with increasing ρ(r c ) while the magnitudes of the curvatures of ρ(r c ) both perpendicular and parallel to the bonds and the Laplacian of ρ(r c ) each increases. These trends are associated with an increase in the electronegativity of the Si cation, a possible increase in the covalent character of the SiO bond and a tendency for SiO(nbr) bonds to be involved in wider OSiO angles than SiO(br) bonds. It is possible, if not likely, that protoanthophyllite has often been misidentified as anthophyllite.  相似文献   

5.
Metamorphic biotites examined by transmission electron microscopy contain planar defects on the (001) plane, superlattices, twins and a microstructure causing streaking of k≠3n rows. Analysis of the fringe contrast shows that the fault vectors associated with the planar defects are either R 1=±1/3 [010], R 2=±1/6 [310] or R 3=±1/6 [3 \(\bar 1\) 0]. Structural considerations indicate that a stacking fault R 1, R 2 or R 3 is most likely to exist in the octahedral layer rather than the potassium layer. The result of such a fault on a unit layer of mica is effectively to rotate it through ±120° about c* (equivalent to the common mica twin law). These stacking faults can provide the mechanism for producing the ±120° rotations associated with the common mica polytypes. Furthermore, many of the observed microstructures can be generated by these stacking faults.  相似文献   

6.
The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr2O3), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr3+ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C 2 or C 2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C 3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D q increases from diopside (1542 cm?1) through omphacite (1552 cm?1), jadeite (1574 cm?1) to spodumene (1592 cm?1). The parameter B which is a measure of covalency for Cr3+-O bonds at M1 sites in clinopyroxene depends on the Cr3+ concentration and the cations at M2 sites.  相似文献   

7.
The mixed valence iron silicate ilvaite, CaFe 2 2+ Fe3+Si2O8(OH), displays electron delocalization associated with Fe2+→Fe3+ charge transfer as observed by Mössbauer spectroscopy. Previous studies report the observation of an ‘electron hopping phenomenon’ with resolution of discrete valence states below 320 K. Mössbauer spectra of a suite of naturally occurring ilvaites were recorded over a temperature range, 80 K to 575 K. Five quadrupole doublets were resolved by computer fitting and assigned to Fe2+(A), Fe2+(B), Fe3+(A), and Fe2+(A)→Fe3+(A)‖c and ⊥c. Contrary to prior work, doublets associated with electron delocalization are resolved at 80 K and preclude the use of a Verwey-type order-disorder model. We propose a thermal activation model and discuss its criteria from molecular orbital and mineralogical viewpoints.  相似文献   

8.
The electron paramagnetic resonance (EPR) spectra of Fe3+ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B 2 0 = 0.112 cm?1, B 2 2 = 0.0688 cm?1 for one and B 2 0 = 0.116 cm?1, B 2 2 = 0.0766 cm?1 for the second. These two spectra arise from Fe3+ substituted for Al3+ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.  相似文献   

9.
Troilite close to FeS, with 0.17 weight percent Cr as main impurity, was obtained from the Agpalilik meteorite. Powder Mössbauer spectroscopy was made in the temperature range 77–645 K. The full Hamiltonian was applied in the fittings. Assuming the asymmetry parameter η to be constant on passing from the high-temperature NiAs-type structure to the medium-temperature MnP-type structure yields a quadrupole splitting (dq=0.5e2 qQ(1+(η2)/3)1/2) value of ?0.25(2) mm/s for these phases. In low-temperature troilite |dq|=0.85 mm/s at room temperature. The combinations of (η, θ, φ) in troilite giving identical spectra range from (0, 49°, -) to (1, 45°, 50°) for negative V zz or from (0.3, 57°, 78°) to (1, 58°, 54°) for positive V zz . Assuming a negative V zz and B‖c gives a θ value in agreement with the shortest Fe-S join being the V zz orientation. The magnetic spin flip of 90° is proposed to occur in the MnP-phase only. The MnP phase-troilite transition occurs at lower temperatures and is more sluggish than in pure FeS.  相似文献   

10.
Multiple scattering of radiation in a semi-infinite electron atmosphere in the absence of true absorption (the Milne problem) is considered. The electron plasma is assumed to be turbulent, i.e., the magnetic field B has a regular B 0 and a stochastic B′ component (B = B 0 + B′). Faraday rotation of the plane of polarization (s8 λ2 B 0 cos gJ) due to the field B 0 depolarizes the outcoming radiation due to the superposition of rays with different polarization-angle rotations, corresponding to different paths traveled before they left the atmosphere. Stochastic Faraday rotation due to isotropic fluctuations, B′, efficiently decreases the amplitude of the polarization of each individual beam as it travels through the turbulent atmosphere. This effect is proportional to λ4 〈(B′)2〉, and becomes the dominant factor at large λ. We use the Ambartsumian-Chandrasekhar invariance principle, which results in six nonlinear equations (for the field B 0 perpendicular to the surface of the medium). We also compute the degree of polarization for the cases B 0 = 0, B′ ≠ 0, and B′ = 0, B 0 ≠ 0, and for a number of versions of the general case, B 0 ≠ 0, B′ ≠ 0. The spectra of the degree of polarization (for the case B 0 = 0) are presented for optical (λ = 0 ? 1 μm), infrared (λ = 1?5 μm), and X-ray (1–50 keV) wavelengths.  相似文献   

11.
57Fe Mössbauer spectra are presented for synthetic cation-deficient Fe2TiO4 and FeCr2O4 spinel particles (<1μm) at various temperatures. The spectra of ferrimagnetic cation-deficient Fe2TiO4 show characteristic features due to relaxation because of superparamagnetism and spin relaxation in the temperature range 5–294 K. At 5 K and 78 K, a superposition of at least two sextets is observed which appear to arise from Fe3+ onA-sites (Fe A 3+ andB-sites (Fe B 3+ ) of the spinal lattice with magnetic hyperfine fields at 5 K ofB hf ((Fe B 3+ )≈47.5 T andB hf (Fe B 3+ )≈51.0 T, respectively. Cation-deficient FeCr2O4 particles reveal at 78 K a fieldB hf (Fe3+)≈46.9 T and exhibit relaxation spectra as a consequence of superparamagnetism in the temperature range 80 K - ～300 K. At 294 K, quadrupole splitting Δ(Fe A 3+ )=0.92 mm/s and isomer shift δ(Fe A 3+ )=0.29 mm/s (relative to metallic Fe) are measured. For both compounds the magnetic hyperfine fieldsB hf are discussed in terms of supertransferred hyperfine fields involving vacancies and in the case of cation-deficient Fe2TiO4 also diamagnetic Ti4+ neighbours of the Fe ions.  相似文献   

12.
The nicotinamide (pyridine-3-carboxamide, nia) complexes of silver(I), [Ag(nia)2(NO3)]·H2O (1), [Ag(nia)2(NO3)] (2), and {K[Ag(nia)2](NO3)2} n (3), were prepared and characterised by IR spectroscopy and TG/DTA thermal methods. The solid state structures of 2 and 3 were determined by single-crystal X-ray diffraction analysis. In both complexes two nicotinamide ligands are coordinated to silver(I) through the nitrogen atom of the pyridine ring in a near-linear fashion. In 2, additional coordination by two oxygen atoms of one nitrate group leads to the distorted tetrahedral coordination environment of silver(I). In 3, nitrate ions bridge potassium cations giving rise to a 2D coordination network which is further stabilised by cross-bridging of each two potassium atoms in [1 0 0] direction by complex cations, [Ag(nia)2]+. Despite different aggregation of 2 and 3 in the solid state, both complexes demonstrate quite similar thermal stability. The amide self-complementary hydrogen bonds appear to be the main driving force for establishing the crystal structures of both 2 and 3.  相似文献   

13.
The abundant iron sulfide mineral pyrite has been shown to catalytically produce hydrogen peroxide (H2O2) and hydroxyl radical ( . OH) in slurries of oxygenated water. Understanding the formation and fate of these reactive oxygen species is important to biological and ecological systems as exposure can lead to deleterious health effects, but also environmental engineering during the optimization of remediation approaches for possible treatment of contaminated waste streams. This study presents the use of the amino acid phenylalanine (Phe) to monitor the kinetics of pyrite-induced . OH formation through rates of hydroxylation forming three isomers of tyrosine (Tyr) - ortho-, meta-, and para-Tyr. Results indicate that about 50% of the Phe loss results in Tyr formation, and that these products further react with . OH at rates comparable to Phe. The overall loss of Phe appeared to be pseudo first-order in [Phe] as a function of time, but for the first time it is shown that initial rates were much less than first-order as a function of initial substrate concentration, [Phe]o. These results can be rationalized by considering that the effective concentration of . OH in solution is lower at a higher level of reactant and that an increasing fraction of . OH is consumed by Phe-degradation products as a function of time. A simplified first-order model was created to describe Phe loss in pyrite slurries which incorporates the [Phe]o, a first-order dependence on pyrite surface area, the assumption that all Phe degradation products compete equally for the limited supply of highly reactive . OH, and a flux that is related to the release of H2O2 from the pyrite surface (a result of the incomplete reduction of oxygen at the pyrite surface). An empirically derived rate constant, K pyr , was introduced to describe a variable . OH-reactivity for different batches of pyrite. Both the simplified first-order kinetic model, and a more detailed numerical simulation, yielded results that compare well to the observed kinetic data describing the effects of variations in concentrations of both initial Phe and pyrite. This work supports the use of Phe as a useful probe to assess the formation of . OH in the presence of pyrite, and its possible utility for similar applications with other minerals.  相似文献   

14.
Fluids at crustal pressures and temperatures   总被引：1，自引：0，他引：1  
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15.
The electron paramagnetic resonance (EPR) spectrum of Cr3+ in synthetic crystals of forsterite consists primarily of lines of Cr3+ “isolated” at the M1 and M2 positions in a “perfect” crystal environment without local charge compensation. In addition it shows two nonequivalent superhyperfine-split sextets with different intensities which are due to strong interaction of the Cr3+ electron spin S (S=3/2) with an adjacent nuclear spin I(I=5/2). Electron nuclear double resonance (ENDOR) experiments revealed that the sextets result from Cr3+ (M1) - Al3+ and Cr3+ (M2) - Al3+ pairs, Al being located at adjacent tetrahedral Si sites. The g, D, A, and A′ tensor components of the Cr3+ - Al3+ pairs have been determined at room temperature. The values of the pairs are distinct although they are not very different from the corresponding data of “isolated” Cr3+. From the intensities of the EPR spectra the relative concentration of the Cr3+ - Al3+ pairs with respect to “isolated” Cr3+ has been estimated.  相似文献   

16.
The cation distribution in the synthetic samples of olivine-type structure with composition (Fe x Mn1?x )2SiO4 was determined at room temperature and confirms previous Mössbauer results. At low temperature an antiferromagnetic ordering is observed. The magnetic structures can be described in the crystallographic cell (i.e. k=0). They are interpreted on the basis of the irreducible representations (modes) of the symmetry groups which are compatible with Pnma. The dominant modes observed for all compounds, including Fe2SiO4 and Mn2SiO4, only differ in their direction. The main direction of magnetization is dominated by the Fe2+ single-ion anisotropy. At 4.2K, for x=0.29, it is parallel to the c-axis, whereas for x=0.76 the direction is parallel to the b-axis. The anisotropy of the M1-sites dominates in the first case, whereas M2-anisotropy dominates in the second case. The influence of temperature is demonstrated for x=0.50 where c is the main direction at 4.2K, when it is b at 38K.  相似文献   

17.
Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm–1 were obtained for the orthorhombic thenardite-type phase Cr2SiO4, unique in its Cr2+-allocation suggesting some metal-metal bonding in Cr2+Cr2+ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr2SiO4, synthesized at 35?kbar, above 1440?°C from high purity Cr2O3, Cr (10% excess) and SiO2 in chromium capsules. The Cr2SiO4-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm–1, in the absorption spectra of Cr2SiO4 single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr2+ in a distorted square planar coordination of point symmetry C2. The crystal field parameter of Cr2+ is estimated to be 10?Dq?10700?cm–1. A relatively intense, sharp band at 18400?cm–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr2+. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr2 4+, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr2+ as well as δ-δ* transitions of Cr2 4+ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Crloc 2+?Cr2, cpl 4+ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.  相似文献   

18.
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19.
The crystal structures of two new compounds (H3O)2[(UO2)(SeO4)2(H2O)](H2O)2 (1, orthorhombic, Pnma, a = 14.0328(18), b = 11.6412(13), c = 8.2146(13) Å, V = 134.9(3) Å3) and (H3O)2[(UO2)(SeO4)2(H2O)](H2O) (2, monoclinic, P21/c, a = 7.8670(12), b = 7.5357(7), c = 21.386(3) Å, β = 101.484(12)°, V = 1242.5(3) Å3) have been solved by direct methods and refined to R 1 = 0.076 and 0.080, respectively. The structures of both compounds contain sheet complexes [(UO2)(SeO4)2]2? formed by cornershared [(UO2)O4(H2O)] bipyramids and SeO4 tetrahedrons. The sheets are parallel to the (100) plane in structure 1 and to (?102) in structure 2. The [(UO2)(SeO4)2(H2O)]2? layers are linked by hydrogen bonds via interlayer groups H2O and H3O+. The sheet topologies in structures 1 and 2 are different and correspond to the topologies of octahedral and tetrahedral complexes in rhomboclase (H2O2)+[Fe(SO4)2(H2O)2] and goldichite K[Fe(SO4)2(H2O)2](H2O)2, respectively.  相似文献   

20.
Mössbauer measurements on neptunite (KNa2Li(Fe,Mn,Mg)2Ti2Si8O24) at 400?K reveal the distribution of Fe-ions on the crystallographic sites in agreement with neutron diffraction results published elsewhere. Even the previously postulated small amount of Fe-ions on the Ti(2) site has been detected, combined with a charge transfer which is in agreement with optical absorption investigations by other authors. A qualitative site occupation model is able to explain the different features of our observations. Single crystal Mössbauer measurements with the k-vector of incident γ-rays parallel to the crystallographic b-axis (space group Cc) of neptunite at different temperatures yield the angle β between the main component of the electric field gradient (EFG), V zz and b. This angle is in close accordance with a calculated value of β for the Fe(1) position from electron density maps. The latter also reveal an absolute value of V zz which is in satisfactory agreement with V zz derived from Mössbauer spectroscopy.  相似文献   

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