A site occupancy analysis of zirconolite CaZrxTi3−xO7

The site occupancies of the zirconolite CaZr_xTi_3?xO₇ over its solid solution range from x≈0.8 to x≈1.30 are determined using Rietveld refinement on X-ray powder diffraction data. A phase analysis of the specimens is also incorporated in the refinement to determine the proportions of zirconolite and any impurity phases present namely TiO₂, ZrO₂ or CaTiO₃. Chemical integrity of the refinement is achieved by constraining the total cation content of each specimen to be the same as the pre-fired starting materials weighed out for each specimen. From the results of the quantitative phase analysis and the observed variation of the lattice parameters, it is established that the solid solution range extends from x=0.83(1) to x=1.33(1). The site occupancy results show that from x=0.83 to x=1 the increase in Zr content is accommodated predominantly on the Zr site up to a saturation value of ～95% Zr. From x=1 up to x=1.2 the additional Zr is absorbed into the Ti(1) and Ti(2) sites, but beyond x=1.2 the Ti(3) site also takes on Zr. Each of these changes in occupancy pattern shows up as an inflection in one or more of the monoclinic lattice parameters and it is possible to identify qualitatively the extent to which changes in each site influences the various lattice parameters.     

On macroseismic attenuation parameters in the comparison of theoretical seismic hazard maps for Southern Calabria and Eastern Sicily (Southern Italy)

For two different zonations of the Calabro-Sicilian region the macroseismic intensity attenuation parameters are computed using the Grandori model.Some modifications to this relation are proposed here in order to allow its applicability also to those cases in which the data set available for each source zone does not present three successive epicentral intensity levels (I ₀) as required for its application.Maps of theoretical distribution of maximum expected intensities were plotted for both zonations adopted, in order to test the reliability, also using other attenuation models.The results of the analysis show how the proposed modifications to the Grandori relation allow the macroseismic intensity attenuation modelling even in cases in which only one intensity level is available.Finally, the comparison of theoretical maximum expected intensity distribution maps, computed for different attenuation models and seismogenic zonations, shows that the maps plotted using the Grandori model and the zonation adopted by G.N.D.T. (Gruppo Nazionale Difesa dai Terremoti - C.N.R. Italy) are more reliable.     

Structure and crystal chemistry of hydrous wadsleyite, Mg1.75SiH0.5O4: possible hydrous magnesium silicate in the mantle transition zone

The crystal structure of hydrous wadsleyite, Mg_1.75SiH_0.5O₄ synthesized in an MA 8-type apparatus at conditions of 1300°C and 15.5 GPa, has been analyzed and refined in space group Imma, using the X-ray intensities measured on a 60X60X10 μm single crystal. The composition (Z=8) and unit cell are Mg_1.74Si_0.97H_0.65O₄ by E.P.M.A. analysis and a=5.663(1) Å, b= 11.546(2) Å, c=8.247(4) Å, V=539.2(5) ų. The partial M-site occupancies were determined; vacancies associated with the incorporation of water are strongly concentrated on the Mg 3 site. The OH in the structure was confirmed by Raman and FTIR spectroscopies. The result of valence sum calculation based on the refined bond lengths indicates that O1 is a hydroxyl. The formula of hydrous wadsleyite can be expressed as Mg_2-xSiH_2xO₄, where 0≤x≤0.25. When x=0.25, all of the O1 site is hydroxyl and the maximum solubility of 3.3 wt% H₂O is realized. Structural relations to other dense hydrous phases are discussed.     

Mössbauer spectroscopic and x-ray powder diffraction studies of synthetic micas on the join annite KFe3AlSi3O10(OH)2-phlogopite KMg3AlSi3O10(OH)2

Micas of the composition K(Fe_3–x Mg _x )AlSi₃ O₁₀(OH)₂ (x=0.6, 1.2, 1.8, 2.4 and 3.0, corresponding to ann₈₀phl₂₀, ann₆₀phl₄₀, ann₄₀phl₆₀, ann₂₀phl₈₀ and ann₀phl₁₀₀) were synthesized hydrothermally under controlled oxygen fugacity conditions. Lattice parameters a ₀ and b ₀ show a distinct linear decrease with increasing Mg content. With increasing ferric iron content a deviation from this linear trend is observed especially within iron rich samples. The tetrahedral rotation angle increases smoothly from 0° in annite to 9.1° in phlogopite. Mössbauer spectra show Fe²⁺ and Fe³⁺ on the octahedral M1 and M2 sites and partially also Fe³⁺ on the tetrahedral site. There is a smooth increase of the quadrupole splitting on both the M1 and the M2 site going from annite to phlogopite, probably due to changes in the lattice contribution to the electric field gradient, assuming a positive correlation between quadrupole splitting and distortion. Fe³⁺ contents, as determined by Mössbauer spectroscopy, versus oxygen fugacity shows that, depending on the composition of the micas, minimum amounts of Fe³⁺ are present. For ann₈₀phl₂₀ this minimum amount of Fe³⁺ is about 8% decreasing to about 1–2% Fe³⁺ for ann₂₀phl₈₀.The molar volume of each solid solution member has been estimated from the determined relations of the molar volume versus % Fe³⁺ contents, extrapolated back to 0% Fe³⁺. Plotting these volumes as a function of X_phl shows that negative excess volume occur in the annitephlogopite join, with the maximum deviation from ideality around X _phl=0.3. Margules volume parameters have been constrained as: Wv, AnnPhl=0.018±0.016 J/(bar.mol) and Wv, PhlAnn=-0.391±0.025 J(bar.mol) (three site basis).     

The inverse problem of the theory of degenerate dwarfs

Based on the radii and masses of degenerate dwarfs derived from HIPPARCOS and other observations, we estimate the microscopic parameters of a Chandrasekhar model (the relativistic parameter at the stellar center x ₀, and the chemical-composition parameter μ _e = A/Z, where A is the mass number and Z is the nuclear charge). We have obtained analytical expressions for the macroscopic characteristics (mass, radius, energy) as functions of x ₀ and μ _e . From the calculated dependence of the energy on these parameters, we have found constraints on the range of variability of x ₀, which are in good agreement with the observed radius distribution of dwarfs. The critical value of x ₀ at which stability breaks down due to general-relativisitc effects is found more accurately than previously. We propose a generalized model with an inhomogeneous (coordinate-dependent) chemical composition, with μ _e = μ _e (r).     

Numerical estimates of mechanical energy transfer from the atmosphere to the Indian ocean

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.     

Re-evaluation of minor events: The examples of the 1895 and 1909 Rome earthquakes

The city of Rome is subjected to moderate seismic risk due to both local and external seismicity. Up to now, the maximum intensity felt has never exceeded VIII MCS. The 1 November 1895 (I _o = VII) and 31 August 1909 (I _o = VI) earthquakes demonstrate that small local events can also cause damage in a large old city. In the present work, we have re-evaluated the intensity values of those two events by means of automatic processing. A comparison between the present results with geological evidence and previous studies is shown, especially for the historical centre of Rome. For the first time, the 1909 earthquake instrumental magnitudeM _L = 3.6 has been calculated from original recordings.     

A combined temperature dependent57Fe Mössbauer and single crystal X-ray diffraction study of synthetic almandine: evidence for the Gol'danskii-Karyagin effect

Synthetic almandine garnet, Fe₃Al₂Si₃O₁₂, has been studied by temperature — dependent single crystal X-ray diffraction and⁵⁷Fe Mössbauer spectroscopy. The Fe²⁺ doublet in almandine is characterized by a small asymmetry between the high and low-velocity peaks that decreases in magnitude with decreasing temperature from 420 to 15 K. The X-ray results show that the Fe²⁺ cation is dynamically disordered with an anisotropic motion within the eight-coordinated site in garnet. The magnitudes of the X-ray determined mean-square-vibrational amplitudes of this motion parallel,x _∥, and perpendicular,x _⊥, to the principle axes of the electric field gradient give a calculated angular dependence of the electric quadrupole interaction of theI _1/2 toI _3/2 transitions that agree with the experimentally measured peak ratios. This is the first recognition of anisotropic recoil free fraction of⁵⁷Fe in silicates.     

Soft X-ray spectroscopy of ferrous silicates

Energy gaps and electrical conductivities in the ferrous silicates, Fe₂SiO₄ and FeSiO₃, depend primarily on Fe-O bonding and may be studied by ultraviolet and soft X-ray spectroscopy. We have measured FeL_II–III X-ray band spectra under conditions of “minimal” (I₄, at 4.0 keV) and “high” (I₁₀, at 10.0 keV) self absorption to determine 3d orbital energy levels, to delineate d states in the valence band, and to construct band gap models. Absorption spectra, I₄/I₁₀, were computed to determine vacant orbital levels in the gap. A difference function (I₄–I₁₀) has been proposed to identify X-radiation at photon energies above the measured L_III absorption edge, including high-energy, double-vacancy satellites and radiative transitions involving the anti-parallel (spin-down) d ⁶ electron in the ground state. The proposed band gap model for Fe₂SiO₄ is consistent with that of Nitsan and Shankland (1976), including an intrinsic transition of 6.5 eV and an energy gap of 7.8 eV. The 3d orbital energy level electronic structures are in general agreement with levels computed by Tossell et al. (1974) for [FeO₆]^10? in FeO using an SCF Xα cluster MO method. A high-energy, double-vacancy satellite was found at ～710.7 eV, and is presumed to originate from an L_IIIM_II,III initial state. The intensity of these satellites for the ferrous silicates and other iron compounds, and corresponding Fe L_II/L_III intensity ratios are correlated with differences in band gap magnitudes and gap structure. Fe L_II/L_III intensity ratios are not well correlated with iron oxidation state.     

Reversal asymmetry in Mesoproterozoic overprinting of the 1.88-Ga Gunflint Formation, Ontario, Canada: non-dipole effects or apparent polar wander?

Eighty-two palaeomagnetic samples of calcareous and jaspilitic grainstones (iron-formation or ‘taconite’) and chert carbonate were collected from the 1.88-Ga Gunflint Formation at 22 sites in the Thunder Bay area, Ontario. Twenty clasts of Gunflint taconite also were sampled from the basal conglomerate of the overlying Mesoproterozoic Sibley Group. Anisotropy of magnetic susceptibility measurements indicate the Gunflint Formation in the sampling area has not experienced regional dynamic metamorphism. Analyses by variable-field translation balance and X-ray diffraction show that the predominant magnetic mineral is hematite but a small amount of magnetite also is present in some samples. Altogether, 213 Gunflint specimens and 59 Sibley conglomerate specimens were subjected to stepwise thermal demagnetisation and 74 Gunflint specimens to stepwise alternating-frequency demagnetisation. The following components were isolated for the taconites:

• Gunflint magnetite: normal declination D=293.4°, inclination I=30.8°, α₉₅=7.2°, n=21; reverse D=86.7°, I=–54.6°, α₉₅=5.8°, n=29.

• Gunflint hematite: normal D=243.6°, I=23.6°, α₉₅=6.0°, n=11; reverse D=70.3°, I=–51.4°, α₉₅=3.2°, n=79.

• Sibley clasts magnetite: normal D=282.7°, I=33.4°, α₉₅=7.6°, n=20.

• Sibley clasts hematite: normal D=254.5°, I=56.2°, α₉₅=8.4°, n=13; reverse D=110.6°, I=–55.7°, α₉₅=8.3°, n=11.

None of these sets passed the reversal test, with the normal component generally being the shallower. Fold tests were negative or inconclusive and the conglomerate test also was negative. Chert carbonate at one other site appears to have acquired a remanence carried by magnetite (D=97.3°, I=−78.2°, α₉₅=6.3°, n=18) prior to folding related to Keweenawan (1.1 Ga) Logan diabase sill emplacement. Most of the components we identified match components for Keweenawan sills, volcanic rocks, intrusions and baked contact rocks in the Thunder Bay area, indicating that Keweenawan magmatism caused widespread chemical remagnetisation of the Proterozoic country rock in our sampling area. Although others have argued that asymmetry was a feature of the Keweenawan geomagnetic field, the declinations of our Gunflint and Sibley hematite and magnetite components are different, suggesting that the components were acquired at significantly different times. We conclude that the reversal asymmetry shown by our Gunflint and Sibley data may best be ascribed to apparent polar wander during Keweenawan times.     

Analysis of macroseismic and instrumental data for the study of the 19 November 1923 earthquake in the Aran Valley (Central Pyrenees)

The 19 November 1923 earthquake in the Aran Valley (Central Pyrenees), with observed maximum intensityI _max = VIII (MSK), has been studied through the compiling and reviewing of macroseismic information and collecting and processing early seismograms. Analysis of macroseismic data gives a focal depth ofh = 5 km and an anelastic attenuation coefficient 10^–3 km^–1. Analysis of early instrumental records allows the computation of estimate of magnitude (M _L = 5.6) and seismic moment (M _o = 1.1 × 10¹⁷ N × m) which are consistent with the values ofI _o andh obtained from macroseismic data.     

地质统计学及其在第四纪研究中的应用

地质统计学是数学地质领域最为活跃而实用的分支,它是以区域化变量理论为基础,以变异函数为基本工具,研究那些在空间分布上既具有随机性又具有结构性的自然现象的科学。在第四纪研究中的很多特征(变量)均可看成区域化变量进行地质统计学分析。作者在讨论了经典概率论及数理统计方法简单地应用于第四纪研究可能出现的问题后,着重介绍了用于第四纪研究中的若干地质统计学方法及基本理论,同时,对地质统计学方法应用于第四纪研究中的前景进行了分析。     

Palaeomagnetism of Cretaceous carbonates from the northwestern part of the Dinaric fold belt

From the island of Cres and the fold belt north of autochthonous Istria 260 light-grey Cretaceous limestone samples were collected at 25 localities. Stepwise thermal demagnetization was employed to clean the remanence up to max. 525 °C. About two-thirds of the samples were successfully cleaned and the locality means were calculated from the characteristic remanences. The locality means significantly deviate from the present field direction both before and after tectonic correction: the mean inclination is about 15° lower than the present inclination and the declination is rotated counterclockwise i.e. it basically fits the pattern so far observed in the Periadriatic region.Unfolding barely influences the scatter of the directions (Cres: D = 308°, I = 45°, k = 26, α₉₅ = 13.3°, before tilt correction, and D = 330°, I = 48°, k = 33, α₉₅ = 11.9° after tilt correction; fold belt north of autochthonous Istria: D = 309°, I = 48°, k = 17, α₉₅ = 11.9°, before tilt correction, and D = 336°, I = 41°, k =13, α₉₅ = 14.0°, after tilt correction. In view of the inconclusive fold test, the magnetization cannot be dated precisely and thus does not yield sufficient information concerning possible relative movements between autochthonous Istria-Gargano and the fold belt studied. Nevertheless, the counterclockwise rotated declinations of the area studied are in contrast with the clockwise rotated declinations of the Ionian Zone of Western Greece. The large angular difference in declination between two parts of the Dalmatian-Ionian Zone with similar tectonic trends casts doubt on the continuity of the fold belt.     

The effect of oxygen vacancies and aluminium substitution on the high-pressure properties of brownmillerite-structured Ca2Fe2?xAlxO5

The structural evolution with pressure and the equations of state of three members of the brownmillerite solid solution, Ca₂(Fe_2−x Al _x )O₅, have been determined by single-crystal X-ray diffraction up to a maximum pressure of 9.73 GPa. The compositions of the samples were x = 0.00 and x = 0.37 (with Pnma symmetry) and x = 0.55 (with I2mb symmetry). No phase transitions were observed in the experiments. The equation of state parameters determined from the pressure-volume data are K _0T = 128.0 (7) GPa, K′₀ = 5.8 (3) for the sample with x = 0.00, K _0T = 131 (2) GPa, K′₀ = 5.5 (4) for x = 0.37, and K _0T = 137.5 (6) GPa, K′₀ = 4 for x = 0.55. The bulk modulus therefore increases with Al content, being 11% higher in the x = 0.55 sample than in the Al-free sample. The unit-cell compression is anisotropic, with the c-axis being stiffer than a or b, and the anisotropy increases with increasing Al content of the structure. The structural response to pressure of all samples is similar. The (Al,Fe)O₄ tetrahedra and the (Al,Fe)O₆ octahedra undergo approximately isotropic compression. There is an increase in the twists of the chains of corner-sharing (Al,Fe)O₄ tetrahedra, and an increase in the tilts of the (Al,Fe)O₆ octahedra, because these framework polyhedra are stiffer than the Ca–O bonds to the extra-framework Ca site. The alignment of the two shortest Ca–O bonds sub-parallel to [001] accounts for the relative stiffness of the c-axis and thus the elastic anisotropy. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Paleomagnetism in Greece: Indications for relative block movement

There is a difference of 120° between the strike of the Pindos mountain chain and that of the Argolis peninsula. Both consist of rocks of the same age (Triassic Jurassic).Samples were collected to see if paleomagnetic data also exhibited this difference in angle. 23 samples from two sites and four lava strata of the Pindos resulted in normal and reversed directions with a mean direction D = 334°, I = 22° with α_95° = 9°, and 24 samples from four sites of the Argolis peninsula in a mean direction of D = 82°, I = 19° with α_95° = 17°. This is a declination difference of D = 108°. Therefore, a relative rotational block movement with an angle of about 110° could be assumed. The result depends to a great extent on the dip correction of the lava flows.     

Calculation of profiles of CIV,NV, OVI,and SiIV resonance lines formed in accretion shocks in T Tauri stars: A plane layer

We have calculated profiles of the CIV 1550, NV 1240, OVI 1035, and SiIV 1400 resonance doublets for a plane-parallel shock viewed at various angles. Calculations were performed for the range of preshock gas velocities V₀ and gas densities ρ₀ appropriate for classical T Tauri stars. The parameters of accretion shocks in young stars can be determined by comparing the calculated and observed profiles of the studied lines and their relative intensities. It is not possible to derive the parameters of the accreting gas from the line profiles without knowing the geometry of the accretion zone. The relation I _v (µ,V₀,ρ₀) for a plane shock, where I _v is the intensity μ=cosθ, can be used to determine the accretion parameters by either choosing a geometry for the radiating region or using a technique similar to Doppler tomography. The results obtained for DR Tau, T Tau, and RY Tau indicate that, in contrast to current concepts, the inner regions of the accretion disk are not disrupted by the magnetic field of the star, and the disk reaches the stellar surface. As a result, only a small fraction of the accreted matter passes through the shock and falls onto the star.     

The variation of tetrahedral bond lengths in sodic plagioclase feldspars

Multiple linear regression analysis has been applied to the geometric and chemical variables in sodic plagioclases in order to determine their relative effects on individual T-O bond lengths in the Al_1+xSi_3?xO₈ tetrahedral framework. Using data from crystal structure analyses of low and high albite, An₁₆ and An₂₈, and assuming that low albite is completely ordered, 1 $$\begin{gathered} {\text{T}} - {\text{O = 1}}{\text{.568}} + {\text{[(0}}{\text{.122) x (Al content of the T site)]}} \hfill \\ {\text{ }} - {\text{[(0}}{\text{.037) x (}}\Delta {\text{{\rm A}l}}_{{\text{br}}} )] + [0.063){\text{ x }}(\Sigma {\text{[}}q{\text{/(Na,Ca}} - {\text{O)}}^{\text{2}} ])] \hfill \\ {\text{ }} + {\text{[(0}}{\text{.029) x (}} - {\text{1/cosT}} - {\text{O}} - {\text{T)]}} \hfill \\ \end{gathered}$$ where the Al content of a particular tetrahedral (T) site can be estimated from empirically-derived determinative curves, where Δ Al_br is a linkage factor to account for the Al content of adjacent tetrahedral sites, where the formal charge on the (Na_1?xCa_x) atom is q=1+x, and where T-O-T is the inter-tetrahedral angle involving the T-O bond. For sodic plagioclases it is essential to know only the anorthite content and the 2Θ₁₃₁-2Θ_1¯31 spacing (CuK _α radiation) in order to determine the independent variables in this equation and thus to evaluate the individual T-O distances. The 64 individual T-O distances predicted for the four sodic plagioclases by this equation agree well with the observed T-O bond lengths (σ=0.004 Å; r=0.994), and the method has been used by way of example to rationalize the T-O bond lengths in analcime (cf. Ferraris, Jones and Yerkess, 1972).     

The crystal and melt structure of spinel and alumina at high temperature: An in-situ XANES study at the Al and Mg K-edge

We present structural information obtained on spinel and alumina at high temperature (298-2400 K) using in-situ XANES at the Mg and Al K-edges. For spinel, ^[4](Al_x,Mg_1−x)^[6](Al_2−x,Mg_x)O_4, with increasing temperature, a substitution of Mg by Al and Al by Mg in their respective sites is observed. This substitution corresponds to an inversion of the Mg and Al sites. There is a significant change in the Al K-edge spectra between crystal and liquid, which can be attributed to a change of the ^[6]Al normally observed in corundum at room temperature, to a mixture of ^[6]Al-^[4]Al in the liquid state. This conclusion is in good agreement with previous ²⁷Al NMR experiments. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.     

OH incorporation in nearly pure MgAl2O4 natural and synthetic spinels

Four nearly pure MgAl₂O₄ spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm⁻¹ indicate an OH content of 90 ppm H₂O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for ^VIO-O_unsh (2.825 Å) and ^IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H₂O. However, at appreciable Fe²⁺ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe²⁺ in the tetrahedral position.     

X—ray Powder Diffraction Characterization of Pyrope

I332／I422，the intensity ratio of powder diffraction,is highly sensitive to variations in garnet compositon and can be taken as an identification criterion for pyrope:I332/I422-1 for pyrope while it is much smaller than unit for other members of the garnet group.