High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.     

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

铝硅酸盐矿物和玻璃中Al的配位与局部结构

利用同步辐射的AlK边X射线吸收近进结构（XANES）谱研究了刚玉和铝硅酸盐矿物（蓝晶石,红柱石,夕线石和钠长石）中Al的配位与局部结构,证明该方法可以作为新的结构探针研究结构未知体系中Al的配位与局部结构。例如,Al的K边XANES谱证明在室温压条件,钠长石玻璃中的Al保持为四面体配位（AlIV）,局部结构与钠长石晶体中的Al相似;尽管硬玉晶体中的Al为八面体配位,但硬玉玻璃中的Al变为四面体配位（AlIV）。而在相同的高温压条件（4．4GPa,1575C）下制备的硬玉-钠长石玻璃系列中,压力引起四面体配位的Al变成五次（Alv）和六次配位（AlVl）,且五次和六次配位Al的比例随玻璃中硬玉含量的增加而增大。     

The orientation and vibrational states of H2O in synthetic alkali-free beryl

 The polarized single-crystal Raman spectra of synthetic H₂O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at room temperature. The H₂O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν₁) at 3607 cm⁻¹ and an IR-active asymmetric stretch (ν₃) at 3700 cm⁻¹ at room temperature. At low temperatures this ν₃ mode is observed in the Raman. Weak ν₁ and ν₃ modes of a second type of H₂O are also observed in the Raman spectra but only at 5 K. The H⋯·H vector of the most abundant type of H₂O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν₁ mode of H₂O are similar to, but not exactly the same as, those of a free H₂O molecule. The Raman measurements indicate that the H₂O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H₂O could be observed as overtones with the internal H₂O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra at ∼200 cm⁻¹. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm⁻¹ in energy (i.e., T_z). The energies of the librational modes are about 210 cm⁻¹ for R_x and 190 cm⁻¹ for R_y. Received: 8 April 1999 / Accepted: 5 April 2000     

Ab-initio calculations of the proton location in topaz-OH,Al<Subscript>2</Subscript>SiO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>

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.     

Scattering pattern analysis and true-amplitude generalized Radon transform migration for acoustic transversely isotropic media with a vertical axis of symmetry

In multi-parameter ray-based anisotropic migration/inversion, it is essential that we have an understanding of the scattering mechanism corresponding to parameter perturbations. Because the complex nonlinearity in the anisotropic inversion problem is intractable, the construction of true-amplitude linearized migration/inversion procedures is needed and important. By using the acoustic medium assumption for transversely isotropic media with a vertical axis of symmetry and representing the anisotropy with P-wave normal moveout velocity, Thomsen parameter δ and anelliptic parameter η, we formalize the linearized inverse scattering problem for three-dimensional pseudo-acoustic equations. Deploying the single-scattering approximation and an elliptically anisotropic background introduces a new linear integral operator that connects the discontinuous perturbation parameters with the multi-shot/multi-offset P-wave scattered data. We further apply the high-frequency asymptotic Green's function and its derivatives to the integral operator, and then the scattering pattern of each perturbation parameter can be explicitly presented. By naturally establishing a connection to generalized Radon transform, the pseudo-inverse of the integral operator can be solved by the generalized Radon transform inversion. In consideration of the structure of this pseudo-inverse operator, the computational implementation is done pointwise by shooting a fan of rays from the target imaging area towards the acquisition system. Results from two-dimensional numerical tests show amplitude-preserving images with high quality.     

基于CALIPSO卫星资料的京津冀地区MODIS卷云云顶高度订正

卷云在大气辐射中扮演着重要角色,对天气系统和气候变化产生重要影响。相比传统地基观测手段,卫星遥感更容易探测到高层卷云的信息,本文利用CALIOP主动遥感仪器可获取较为准确的薄卷云特性的特点,针对MODIS被动遥感探测器反演的薄卷云云顶高度的偏差开展订正研究。研究选取2013～2017年京津冀地区MODIS云产品,结合CALIPSO卫星的卷云云顶高度数据,基于交叉验证的方法得到线性拟合方案,对MODIS卷云云顶高度进行订正。订正后的MODIS与CALIPSO卷云云顶高度差值的分布区间由?3～2 km变为?2.0～2.5 km,峰值由?0.8 km左右变为0.2 km左右。订正效果随云顶高度和云光学厚度的不同有所变化,其中较低层卷云和光学薄卷云的订正效果更明显。     

Measurements of tropospheric OH concentrations: A comparison of field data with model predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×10⁶ to 3.2×10⁶ cm^-3. Simultaneously we measured the concentrations of O₃, H₂O, NO, NO₂, CH₄, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O₃ and NO₂. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO _x concentrations. It is argued that additional, so far unidentified. HO _x loss reactions must be responsible for that discrepancy.     

Imaging spectroscopy in soil-water based site suitability assessment for artificial regeneration to Scots pine

In a humid northern boreal climate, the success rate of artificial regeneration to Scots pine (Pinus sylvestris L.) can be improved by including a soil water content (SWC) based assessment of site suitability in the reforestation planning process. This paper introduces an application of airborne visible-near-infrared imaging spectroscopic data to identify suitable subregions of forest compartments for the low SWC-tolerant Scots pine. The spatial patterns of understorey plant species communities, recorded by the AISA (Airborne Imaging Spectrometer for Applications) sensor, were demonstrated to be dependant on the underlying SWC. According to the nonmetric multidimensional scaling and correlation results twelve understorey species were found to be most abundant on sites with high soil SWCs. The abundance of bare soil, rocks and abundance of more than ten species indicated low soil SWCs. The spatial patterns of understorey are attributed to time-stability of the underlying SWC patterns. A supervised artificial neural network (radial basis functional link network, probabilistic neural network) approach was taken to classify AISA imaging spectrometer data with dielectric (as a measure volumetric SWC) ground referencing into regimes suitable and unsuitable for Scots pine. The accuracy assessment with receiver operating characteristics curves demonstrated a maximum of 74.1% area under the curve values which indicated moderate success of the NN modelling. The results signified the importance of the training set’s quality, adequate quantity (>2.43 points/ha) and NN algorithm selection over the NN algorithm training parameter optimization to perfection. This methodology for the analysis of site suitability of Scots pine can be recommended, especially when artificial regeneration of former mixed wood Norway spruce (Picea abies L. Karst) - downy birch (Betula pubenscens Ehrh.) stands is being considered, so that artificially regenerated areas to Scots pine can be optimized for forestry purposes.