Hydrogen sites in the dense hydrous magnesian silicate phase E: a pulsed neutron powder diffraction study

Hydrogen site positions and occupancy in the crystal structure of dense hydrous magnesium silicate (DHMS) phase E were determined for the first time by pulsed neutron powder diffraction. A fully deuterated pure phase E powder sample, which had space group \(R\overline{3} m\) and lattice parameters of a = 2.97065(8) Å and c = 13.9033(4) Å, was synthesized at 15 GPa and 1100 °C. Through quantitative evaluation of refined structure parameters obtained with sufficient spatial resolution and very high signal-to-background ratio, we conclude that the O–D dipoles in the refined phase E structure are tilted by 24° from the direction normal to the layers of edge-shared MgO₆ octahedra (octahedral layers). The tilted dipole structure of phase E is in remarkable contrast to that of brucite, Mg(OH)₂, which has dipoles exactly normal to the octahedral layer. This contrast exists because the O–Si–O bonding unique in the phase E structure connects two adjacent octahedral layers and thereby reduces the interlayer O···O distance. This shrinkage of the interlayer distance induces the tilting of the O–D dipole and also generates unique O–D···O hydrogen bonding connecting all the layers in the phase E structure.     

Thermal equation of state of natural tourmaline at high pressure and temperature

Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K ₀ = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α ₀ = 4.39 (27) × 10^?5 K^?1 and temperature derivative of the bulk modulus (?K/?T) _P  = ?0.009 (6) GPa K^?1 were obtained. The axial thermoelastic properties were also obtained with K _a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α _a0 = 1.00 (11) × 10^?5 K^?1 for the a-axis, and K _c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α _c0 = 2.41 (24) × 10^?5 K^?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.     

Phase relation of CaSO<Subscript>4</Subscript> at high pressure and temperature up to 90 GPa and 2300 K

Calcium sulfate (CaSO₄), one of the major sulfate minerals in the Earth’s crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO₄ up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO₄ forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO₄-type structure or another modified barite structure depending on pressure. We obtained the pressure–volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P–T conditions. This suggests that CaSO₄ is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate–sulfide speciation may play a major role in the sulfur recycling into the deep Earth.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Anisotropic mechanical properties of zircon and the effect of radiation damage

This study provides new insights into the relationship between radiation-dose-dependent structural damage due to natural U and Th impurities and the anisotropic mechanical properties (Poisson’s ratio, elastic modulus and hardness) of zircon. Natural zircon samples from Sri Lanka (see Muarakami et al. in Am Mineral 76:1510–1532, 1991) and synthetic samples, covering a dose range of zero up to 6.8 × 10¹⁸ α-decays/g, have been studied by nanoindentation. Measurements along the [100] crystallographic direction and calculations, based on elastic stiffness constants determined by Özkan (J Appl Phys 47:4772–4779, 1976), revealed a general radiation-induced decrease in stiffness (~54 %) and hardness (~48 %) and an increase in the Poisson’s ratio (~54 %) with increasing dose. Additional indentations on selected samples along the [001] allowed one to follow the amorphization process to the point that the mechanical properties are isotropic. This work shows that the radiation-dose-dependent changes of the mechanical properties of zircon can be directly correlated with the amorphous fraction as determined by previous investigations with local and global probes (Ríos et al. in J Phys Condens Matter 12:2401–2412, 2000a; Farnan and Salje in J Appl Phys 89:2084–2090, 2001; Zhang and Salje in J Phys Condens Matter 13:3057–3071, 2001). The excellent agreement, revealed by the different methods, indicates a large influence of structural and even local phenomena on the macroscopic mechanical properties. Therefore, this study indicates the importance of acquiring better knowledge about the mechanical long-term stability of radiation-damaged materials.     

Upper-Tropospheric Environment–Tropical Cyclone Interactions over the Western North Pacific: A Statistical Study

Based on 25-year(1987–2011) tropical cyclone(TC) best track data, a statistical study was carried out to investigate the basic features of upper-tropospheric TC–environment interactions over the western North Pacific. Interaction was defined as the absolute value of eddy momentum flux convergence(EFC) exceeding 10 m s~(-1)d~(-1). Based on this definition, it was found that 18% of all six-hourly TC samples experienced interaction. Extreme interaction cases showed that EFC can reach~120 m s~(-1)d~(-1) during the extratropical-cyclone(EC) stage, an order of magnitude larger than reported in previous studies.Composite analysis showed that positive interactions are characterized by a double-jet flow pattern, rather than the traditional trough pattern, because it is the jets that bring in large EFC from the upper-level environment to the TC center. The role of the outflow jet is also enhanced by relatively low inertial stability, as compared to the inflow jet. Among several environmental factors, it was found that extremely large EFC is usually accompanied by high inertial stability, low SST and strong vertical wind shear(VWS). Thus, the positive effect of EFC is cancelled by their negative effects. Only those samples during the EC stage, whose intensities were less dependent on VWS and the underlying SST, could survive in extremely large EFC environments, or even re-intensify. For classical TCs(not in the EC stage), it was found that environments with a moderate EFC value generally below ~25 m s~(-1)d~(-1) are more favorable for a TC's intensification than those with extremely large EFC.     

Preface to the Special Issue “Unified Perspective of Climate Variability and Change”

正Forty years ago,Klaus Wyrtki(1975)of University of Hawaii discovered that El Nino warming off South America is not a result of local wind change but a response to the relaxed equatorial trade winds some 10 000 km away near the international dateline.The Kelvin wave mechanism was quickly verified from wind-forced ocean model simulations.Consequent     

Characteristics of the Asian–Pacific Oscillation in Boreal Summer Simulated by BCC_CSM with Different Horizontal Resolutions

The summer Asian–Pacific Oscillation(APO) is a major teleconnection pattern that reflects the zonal thermal contrast between East Asia and the North Pacific in the upper troposphere. The performance of Beijing Climate Center Climate System Models(BCC CSMs) with different horizontal resolutions, i.e., BCC CSM1.1 and BCC CSM1.1(m), in reproducing APO interannual variability, APO-related precipitation anomalies, and associated atmospheric circulation anomalies, is evaluated.The results show that BCC CSM1.1(m) can successfully capture the interannual variability of the summer APO index. It is also more capable in reproducing the APO's spatial pattern, compared to BCC CSM1.1, due to its higher horizontal resolution. Associated with a positive APO index, the northward-shifted and intensified South Asian high, strengthened extratropical westerly jet, and tropical easterly jet in the upper troposphere, as well as the southwesterly monsoonal flow over North Africa and the Indian Ocean in the lower troposphere, are realistically represented by BCC CSM1.1(m), leading to an improvement in reproducing the increased precipitation over tropical North Africa, South Asia, and East Asia, as well as the decreased precipitation over subtropical North Africa, Japan, and North America. In contrast, these features are less consistent with observations when simulated by BCC CSM1.1. Regression analysis further indicates that surface temperature anomalies over the North Pacific and the southern and western flanks of the Tibetan Plateau are reasonably reproduced by BCC CSM1.1(m), which contributes to the substantial improvement in the simulation of the characteristics of summer APO compared to that of BCC CSM1.1.     

Incorporation of a dynamic root distribution into CLM4.5: Evaluation of carbon and water fluxes over the Amazon

Roots are responsible for the uptake of water and nutrients by plants and have the plasticity to dynamically respond to different environmental conditions. However, most land surface models currently prescribe rooting profiles as a function only of vegetation type, with no consideration of the surroundings. In this study, a dynamic rooting scheme, which describes root growth as a compromise between water and nitrogen availability, was incorporated into CLM4.5 with carbon–nitrogen(CN) interactions(CLM4.5-CN) to investigate the effects of a dynamic root distribution on eco-hydrological modeling. Two paired numerical simulations were conducted for the Tapajos National Forest km83(BRSa3) site and the Amazon, one using CLM4.5-CN without the dynamic rooting scheme and the other including the proposed scheme. Simulations for the BRSa3 site showed that inclusion of the dynamic rooting scheme increased the amplitudes and peak values of diurnal gross primary production(GPP) and latent heat flux(LE) for the dry season, and improved the carbon(C) and water cycle modeling by reducing the RMSE of GPP by 0.4 g C m~(-2)d~(-1), net ecosystem exchange by 1.96 g C m~(-2)d~(-1), LE by 5.0 W m~(-2), and soil moisture by 0.03 m~3m~(-3), at the seasonal scale, compared with eddy flux measurements, while having little impact during the wet season. For the Amazon, regional analysis also revealed that vegetation responses(including GPP and LE) to seasonal drought and the severe drought of 2005 were better captured with the dynamic rooting scheme incorporated.     

The Upstream “Strong Signals” of the Water Vapor Transport over the Tibetan Plateau during a Heavy Rainfall Event in the Yangtze River Basin

A heavy rainfall event that occurred over the middle and lower reaches of the Yangtze River Basin(YRB) during July11–13 2000 is explored in this study. The potential/stream function is used to analyze the upstream "strong signals" of the water vapor transport in the Tibetan Plateau(TP). The studied time period covers from 2000 LST 5 July to 2000 LST 15 July(temporal resolution: 6 hours). By analyzing the three-dimensional structure of the water vapor flux, vorticity and divergence prior to and during the heavy rainfall event, the upstream "strong signals" related to this heavy rainfall event are revealed. A strong correlation exists between the heavy rainfall event in the YRB and the convective clouds over the TP. The "convergence zone" of the water vapor transport is also identified, based on correlation analysis of the water vapor flux two days and one day prior to, and on the day of, the heavy rainfall. And this "convergence zone" coincides with the migration of the maximum rainfall over the YRB. This specific coupled structure actually plays a key role in generating heavy rainfall over the YRB. The eastward movement of the coupled system with a divergence/convergence center of the potential function at the upper/lower level resembles the spatiotemporal evolution of the heavy rainfall event over the YRB. These upstream "strong signals" are clearly traced in this study through analyzing the three-dimensional structure of the potential/stream function of upstream water vapor transport.