Si and O self-diffusion in hydrous forsterite and iron-bearing olivine from the perspective of defect chemistry

We discuss the experimental results of silicon and oxygen self-diffusion coefficients in forsterite and iron-bearing olivine from the perspective of defect chemistry. Silicon diffusion is dominated by V_O ^··-associated V_Si″″, whereas oxygen diffusion is dominated by hopping of V_O ^·· under anhydrous conditions, and by (OH)_O ^· under hydrous conditions. By considering the charge neutrality condition of [(OH)_O ^·] = 2[V_Me″] in hydrous forsterite and iron-bearing olivine, we get D _Si ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))^1/3 and D _O ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))⁰, which explains the experimental results of water effects on oxygen and silicon self-diffusion rates (Fei et al. in Nature 498:213–215, 2013; J Geophys Res 119:7598–7606, 2014). The \(C_{{{\text{H}}_{2} {\text{O}}}}\) dependence of creep rate in the Earth’s mantle should be close to that given by Si and O self-diffusion coefficients obtained under water unsaturated conditions.     

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.     

Geological development of Heard Island,Central Kerguelen Plateau

We report ⁴⁰Ar–³⁹Ar laser step-heating age determinations on 15 stratigraphically controlled lava flows and intrusive rocks from Heard Island, Central Kerguelen Plateau (Indian Ocean). The island history began with uplift of pelagic limestone intruded by 22 Ma gabbro sills. Subaerial and wave erosion levelled the early island, producing an unconformity onto which pillow lavas, tuffaceous sediments and shallow-water, fossiliferous marine siltstone (Drygalski Formation) were deposited, beginning in late Miocene time. Two volcanic systems then formed in the late Quaternary. Big Ben dominates the larger southeast part of the island, while Mount Dixon occupies the northwest Laurens Peninsula. Feeder dykes and the early lava flows in both systems are 400–200 ka. Lava flows with evolved compositions (trachytes, trachyandesites) erupted 100–20 ka. Well-preserved parasitic cones exposed at low elevations are 15–10 ka and younger. Mawson Peak, near the summit of Big Ben, has erupted lava flows as recently as 2007. Heard Island, and nearby active McDonald Island, are subaerial features of a larger Neogene volcanic region of Central Kerguelen Plateau that includes several large sea knolls and recently identified submarine fields of small cones. This broadly distributed volcanic activity is linked to incubation of plume material at the base of the nearly stationary overlying Central Kerguelen Plateau.     

The impact of boreal autumn SST anomalies over the South Pacific on boreal winter precipitation over East Asia

The possible mechanism behind the variability in the dipole pattern of boreal winter precipitation over East Asia is analyzed in this study. The results show that the SST anomalies(SSTAs) over the South Pacific Ocean(SPO) in boreal autumn are closely related to the variability in the dipole pattern of boreal winter precipitation over East Asia. The physical link between the boreal autumn SPO SSTAs and the boreal winter East Asian precipitation dipole pattern is shown to mainly be the seasonal persistence of the SPO SSTAs themselves. The seasonal persistence of the SPO SSTAs can memorize and transport the signal of the boreal autumn SSTAs to the following winter, and then stimulates a meridional teleconnection pattern from the SH to the NH, resulting in a meridional dipole pattern of atmospheric circulation over East Asia in boreal winter. As a major influencing factor, this dipole pattern of the atmospheric circulation can finally lead to the anomalous precipitation dipole pattern over East Asia in boreal winter. These observed physical processes are further confirmed in this study through numerical simulation. The evidence from this study, showing the impact of the SPO SSTAs in boreal autumn,not only deepens our understanding of the variability in East Asian boreal winter precipitation, but also provides a potentially useful predictor for precipitation in the region.     

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