Crystal chemistry, thermal expansion, and Raman spectra of hydroxyl-clinohumite: implications for water in Earth’s interior

Two samples of hydroxyl-clinohumite, sample SZ0407B with approximate composition Mg_8.674(14)Fe_0.374(4)(Si_0.99(1)O₄)₄(OH)₂ and sample SZ0411B with composition Mg₉(SiO₄)₄(OH)₂, were synthesized at 12 GPa and 1,250 °C coexisting with olivine. Unit-cell parameters determined by single-crystal X-ray diffraction are given as follows: a = 4.7525(4) Å, b = 10.2935(12) Å, c = 13.7077(10) Å, α = 100.645(9)°, V = 659.04(9) Å³ for SZ0407B, and a = 4.7518(6) Å, b = 10.2861(12) Å, c = 13.7008(9) Å, α = 100.638(9)°, V = 658.15(9) Å³ for SZ0411B. Single-crystal X-ray intensity data were collected for crystal structure refinements of both samples. Relative to the pure-Mg sample, Fe decreases M3–OH bond lengths by ~0.010(3) Å, consistent with some ferric iron ordering into M3. Raman spectroscopy shows two strong bands in the lattice-mode region at 650 and 690 cm^?1 in the Fe-bearing sample, which are not observed in the pure-Mg sample. Spectra in the H₂O region show at least five bands, which are deconvolved into seven distinct O–H-stretching modes. Thermal expansion measurements were carried out for both samples from 153 to 787 K by single-crystal X-ray diffraction. The average a-, b-, c-axial and volumetric thermal expansion coefficients (10^?6 K^?1) are 10.5(1), 12.3(2), 12.5(2) and 34.9(5) for SZ0407B, respectively, and 11.1(1), 12.6(3), 13.7(3), 36.8(6) for SZ0411B, respectively. After heating, the unit-cell parameters were refined again for each sample at ambient condition, and no significant changes were observed, indicating no significant oxidation or dehydration during the experiment. For the DHMS phases along the brucite–forsterite join, linear regression gives a systematic linear decrease in expansivity with increasing density. Further, substitution of ferrous iron into these structures decreases thermal expansivity, making the Fe-bearing varieties slightly stiffer.     

Topographic change and numerically modelled near surface wind flow in a bowl blowout

A number of studies have measured and numerically modelled near surface wind velocity over a range of aeolian landforms and made suppositions about topographic change and landform evolution. However, the precise measurement and correlation of flow dynamics and resulting topographic change have not yet been fully realized. Here, using repeated high-resolution terrestrial laser scanning and numerical flow modelling within a bowl blowout, we statistically analyse the relationship between wind speed, vertical wind velocity, turbulent kinetic energy and topographic change over a 33-day period. Topographic results showed that erosion and deposition occurred in distinct regions within the blowout. Deposition occurred in the upwind third of the deflation basin, where wind flow became separated and velocity and turbulent kinetic energy decreased, and erosion occurred in the downwind third of the deflation basin, where wind flow reattached and aligned with incident wind direction. Statistical analysis of wind flow and topographic change indicated that wind speed had a strong correlation with overall topographic change and that vertical wind velocity (including both positive and negative) displayed a strong correlation with negative topographic change (erosion). Only weak or very weak correlations exist for wind flow parameters and positive topographic change (accretion). This study demonstrates that wind flow modelling using average incident wind conditions can be utilized successfully to identify regions of overall change and erosion for a complex aeolian landform, but not to identify and predict regions where solely accretion will occur. © 2019 John Wiley & Sons, Ltd.     

Site occupancies of minor elements in synthetic olivines as determined by channeling-enhanced X-ray emission

Major- and minor-element site occupancies have been determined for Ni- and Mn-rich synthetic forsteritic olivines that were equilibrated to 300, 600, 900, or 1,050° C, by analyzing electron-channeling-enhanced x-ray emissions. Site preferences for minor elements (Ni>Cr for M1; Ca>Mn for M2) are consistent with those reported in previous studies. Degrees of ordering at different elevated temperatures differ less than analytical errors, although there may be significant differences in ordering between olivines that have been rapidly quenched from 300° C or higher and those that have undergone normal lava-flow cooling histories. An x-ray structure refinement of San Carlos olivine (R=0.031) gives major-element occupancies similar to those determined by electron-channeling on the same material. Thus, the channeling technique gives results that are consistent with other methods, and it may be possible to use the technique to identify olivines that have undergone very rapid quenching.     

Raman spectroscopic study of hydrous <Emphasis Type="Italic">γ</Emphasis>-Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> to 56.5 GPa

 Raman spectra of a single-crystal fragment of hydrous γ-Mg₂SiO₄, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure, showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency of the new mode (802 cm⁻¹ extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range for ringwoodite in the mantle. Received: 7 December 2001 / Accepted: 16 April 2002     

Remote sensing of sea surface temperature and chlorophyll during Lagrangian experiments at the Iberian margin

Satellite derived sea surface temperature (SST) and chlorophyll data are used to characterise the period of upwelling during a cruise on which two Lagrangian drift experiments were conducted off the Iberian Atlantic coast in August 1998. During the cruise there was a prolonged period of equator-ward winds which favour upwelling; three distinct maxima were observed in the meteorological data interspersed with periods of relaxation. The SST and chlorophyll imagery show upwelling to be active with distinct offshore filaments that are cooler and of higher chlorophyll concentration than the surrounding oceanic water; these filaments represent an important cross-shelf transport mechanism. A front detection methodology has been applied to satellite images and suggests that these filaments are distinct, long-lived features, characterised by enhanced primary production.     

The sodium and hydrogen gas clouds of Io

Models are developed to describe the spatial distribution of gases emitted by Io and are applied to recent observations which indicate extensive gas clouds of hydrogen and sodium in orbit around Jupiter. Hydrogen and sodium atoms are emitted from Io with velocities in the range 2 to 3 km sec^?1, with fluxes of about 10¹⁰ and 10⁸cm^?2sec^?1 for hydrogen and sodium respectively. Hydrogen atoms may be formed by photodecomposition of gases such as NH₃ or H₂S released from the satellite surface and may escape thermally from an exosphere whose temperature is about 500 K. Sodium may be ejected from the surface by energetic particles or by ultraviolet radiation and it appears that a non-thermal mechanism drawing energy from Jupiter's magnetic field is required in order to account for its release to space.     

Jet flow over foredunes

Jet flows, which are localized flows exhibiting a high speed maxima, are relatively common in nature, and in many devices. They have only been occasionally observed on dunes, and their dynamics are poorly known. This paper examines computational fluid dynamic (CFD) two‐dimensional (2D) modelling of jet flow over a foredune topography. Flow was simulated in 10° increments from onshore (0°) to highly oblique alongshore (70°) incident wind approach angles. CFD modelling reveals that the formation of a jet is not dependent on a critical wind speed, and an increase in incident wind velocity does not affect the magnitude of jet flow. A jet is first formed at ~1.0 m seawards of the foredune crest on the Prince Edward Island foredune morphology example examined here. A jet is not developed when the incident wind is from an oblique approach angle greater than ~50° because there is significantly less flow acceleration across a much lower slope at this incident angle. The presence of a scarp does influence the structure of the crest jet, in that the jet is more pronounced where a scarp is present. Surface roughness affects the magnitude of jet expansion and jets are better developed on bare surfaces compared to vegetated ones. Copyright © 2016 John Wiley & Sons, Ltd.     

Sequence in Australian coal seams

An embedded Markov model is used to test microlithotype analyses of subsections of a wide range of Australian coal seams for the presence of nonrandom sequences of lithologies. The data for individual seams, transformed to give five states (four states if dirt bands are excluded),were summed into geologically and geographically distinct groupings. The results suggest that dirt bands form an essential part of the sequences and that partial or complete cyclicity is present in many seam groupings. The cyclicity is either asymmetric or partially symmetric with the vitrite +clarite content of the coal decreasing upwards within each cycle. A new cycle is marked either by a sharp reversion, or by a slightly gradational reversion, to a vitrite +clariterich lithology. This reversion may or may not be preceded by a dirt band. In virtually all groupings, a vitrite +clarite-rich lithology is the most likely type after a dirt band. The sequences are similar to those that have been described in European coals and it seems probable that the presence of intraseam, cyclic sequences is a normal, rather than an unusual condition, within coal seams. This cyclicity is a response to changes in the sedimentation balance. These changes are probably due in large part to processes originating within the peat-forming environment but processes external to this environment are also likely to produce cyclic sequences of coal lithologies.     

High-pressure Raman spectroscopic study of Fo90 hydrous wadsleyite

Raman spectra of monoclinic Fo₉₀ hydrous wadsleyite with 2.4 wt% H₂O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm⁻¹ and the symmetric stretch of the SiO₃ unit at 918 cm⁻¹, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo₉₀ hydrous and Fo₁₀₀ anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo₉₀ hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm⁻¹ at 1-bar and shifted to 500–850 cm⁻¹ at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo₉₀ hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo₉₀ and Fo₁₀₀ hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm⁻¹ decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm⁻¹ is consistent with protons being located at the O1···O edges around M3.