Octahedral cation ordering in olivine at high temperature. I: in situ neutron single-crystal diffraction studies on natural mantle olivines (Fa12 and Fa10)

Crystallographic determinations on natural olivine single crystals of mantle composition and origin, carried out by in situ neutron diffraction at high temperature, show that the octahedrally co-ordinated Fe²⁺ and Mg cations undergo two successive trends of cation ordering with increasing temperature. An initial slight preference of Fe²⁺ for site M1, up to a temperature of about 850?°C, is followed by a reverse-ordering reaction with a site preference exchange between the two cations. The cross-over between the two regimes of ordering, corresponding to a situation of complete disorder, occurs at about 900?°C. Above this temperature Fe²⁺ progressively and strongly segregates into site M2 up to 1300?°C, the practical limit of the experimental setup utilized in the experiments. Care was taken to ensure that no chemical changes occurred in the crystals (i.e. oxidation), as testified by Mössbauer spectroscopy determinations carried out before and after the heat treatment. The cation-ordering behaviour is reflected in temperature-dependent changes of geometrical and atomic displacement parameters occurring in the octahedral sites M1 and M2. A thermodynamical explanation of this behaviour is proposed in terms of a prevailing vibrational contribution to entropy.     

William Gilbert: the first palaeomagnetist

William Gilbert first described the Earth as a giant dipole magnet 400 years ago. But, as Rod Wilson recounts, he did far more than this.     

New views of Betelgeuse: multi-wavelength surface imaging and implications for models of hotspot generation

We report contemporaneous multi-wavelength interferometric imaging of the red supergiant star Betelgeuse ( α Orionis), using the Cambridge Optical Aperture Synthesis Telescope (COAST) and the William Herschel Telescope (WHT), at wavelengths of 700, 905 and 1290 nm. We find a strong variation in the apparent symmetry of the stellar brightness distribution as a function of wavelength. At 700 nm the star is highly asymmetric, and can be modelled as the superposition of three bright spots on a strongly limb-darkened disc. However, at 905 nm only a single low-contrast feature is visible and at 1290 nm the star presents a featureless symmetric disc. The change in spot contrast with wavelength is consistent with a model in which the bright spots represent unobscured areas of elevated temperature, owing perhaps to convection, on a stellar disc that itself has a different appearance, i.e. geometrical extent and limb-darkening profile, at different wavelengths. The featureless centre-to-limb brightness profile seen at 1290 nm is consistent with this model and suggests that future interferometric monitoring of the star to quantify the size changes associated with radial velocity variations should be performed at similar wavelengths in the near-infrared.     

A laser beacon for monitoring the mesospheric sodium layer at La Palma

We report the results of the first laser beacon experiment at the astronomical site of La Palma (Canary Islands). A continuous wave low‐power laser (a few hundred mW) system has been set up. The laser, tuned on the sodium D₂ line at 589 nm, is launched close to the zenith angle. The emission of the mesospheric sodium layer is observed from a telescope located 160 m away from the laser. The layer is therefore resolved in altitude and the different features of its dynamics are investigated.     

Surface and complexation effects on the rate of Mn(II) oxidation in natural waters

Montmorillonite, kaolinite, goethite, and particulate and soluble natural organic materials influence the rate of Mn(II) oxidation. While surfaces accelerate the reaction, apparently by bonding Mn²⁺ in a manner which fulfills the requirements of the transition state, soluble organic materials retard the reaction by complexing the oxidizable species. It is doubtful whether particulate matter would influence the oxidation process under natural loading conditions since 50–500 mg l^?1quantities are required to produce measurable changes in the reaction rate. Complexation by humic materials, however, might be expected to reduce the rate of oxidation by an amount proportional to the dissolved organic carbon concentration. Oxidation followed by precipitation is predicted to be an important mechanism for Mn²⁺ removal in oceanic waters. The situation is less predictable in lake waters.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

Magnitudes, spatial scales and processes of environmental antimony mobility from orogenic gold–antimony mineral deposits, Australasia

Antimony (Sb) is strongly concentrated into hydrothermal mineral deposits, commonly with gold, in metasedimentary sequences around the Pacific Rim. These deposits represent potential point sources for Sb in the downstream environment, particularly when mines are developed. This study documents the magnitude and scale of Sb mobility near some mineral deposits in Australia and New Zealand. Two examples of New Zealand historic mining areas demonstrate that natural groundwater dissolution of Sb from mineral deposits dominates the Sb load in drainage waters, with Sb concentrations between 3 and 24 μg/L in major streams. Mine-related discharges can exceed 200 μg/L Sb, but volumes are small. Sb flux in principal stream waters is ca 1–14 mg/s, compared to mine tunnel fluxes of ca 0.001 mg/s. Dissolved Sb is strongly attenuated near some mine tunnels by adsorption on to iron oxyhydroxide precipitates. Similar Sb mobilisation and attenuation processes are occurring downstream of the historic/active Hillgrove antimony–gold mine of New South Wales, Australia, but historic discharges of Sb-bearing debris has resulted in elevated Sb levels in stream sediments (ca 10–100⁺ mg/kg) and riparian plants (up to 100 mg/kg) for ca 300 km downstream. Dissolution of Sb from these sediments ensures that river waters have elevated Sb (ca 10–1,000 μg/L) over that distance. Total Sb flux reaching the Pacific Ocean from the Hillgrove area is ca 8 tonnes/year, of which 7 tonnes/year is particulate and 1 tonne/year is dissolved.     

Post-collisional, K-rich mafic magmatism in south Tibet: constraints on Indian slab-to-wedge transport processes and plateau uplift

Post-collisional (23–8 Ma), potassium-rich (including ultrapotassic and potassic) mafic magmatic rocks occur within the north–south-trending Xuruco lake–Dangre Yongcuo lake (XDY) rift in the Lhasa terrane of the southern Tibetan Plateau, forming an approximately 130-km-long semi-continuous magmatic belt. They include both extrusive and intrusive facies. Major and trace element and Sr–Nd–Pb isotopic data are presented for all of the known exposures within the XDY rift. The potassium-rich, mafic igneous rocks are characterized by high MgO (5.9–10.8 wt.%), K₂O (4.81–10.68 wt.%), Ba (1,782–5,618 ppm) and Th (81.3–327.4 ppm) contents, and relatively high SiO₂ (52.76–58.32 wt.%) and Al₂O₃ (11.10–13.67 wt.%). Initial Sr isotopic compositions are extremely radiogenic (0.712600–0.736157), combined with low (²⁰⁶Pb/²⁰⁴Pb) _i (18.28–18.96) and (¹⁴³Nd/¹⁴⁴Nd) _i (0.511781–0.512046). Chondrite-normalized rare earth element patterns display relatively weak negative Eu anomalies. Primitive mantle-normalized incompatible trace element patterns exhibit strong enrichments in large ion lithophile elements relative to high-field-strength elements and display strongly negative Ta–Nb–Ti anomalies. The combined major and trace element and Sr–Nd–Pb isotopic characteristics of the K-rich igneous rocks suggest that the primitive magmas were produced by 1–10 % partial melting of an asthenospheric mantle source enriched by both fluids and partial melts derived from Indian passive continental margin sediments subducted into the shallow mantle as a consequence of the northward underthrusting of the Indian continental lithosphere beneath Tibet since the India–Asia collision at ~55 Ma. The best-fit model results indicate that a melt with trace element characteristics similar to those of the K-rich rocks could be generated by 8–10 % partial melting of a metasomatized mantle source in the south and 1–2 % melting in the north of the XDY rift. Trace element and Sr–Nd–Pb isotopic modeling indicate that the proportion of fluid derived from the subducted sediments, for which we use as a proxy the Higher Himalayan Crystalline Sequence (HHCS), in the mantle source region increases from north (rear-arc) to south (front-arc), ranging from 0 to 5 %, respectively. Correspondingly, the proportion of the melt derived from the subducted HHCS in the source increases from north (2 %) to south (15 %). The increasing proportion of the fluid and melt component in the mantle source from north to south, together with a southward decreasing trend in the age of the K-rich magmatism within the XDY rift, is inferred to reflect rollback of the subducted Indian lithospheric mantle slab during the period 25–8 Ma. Slab rollback may be linked to a decreasing convergence rate between India and Asia. As a consequence of slab rollback at 25 Ma beneath the Lhasa terrane, its geodynamic setting was transformed from a convergent (55–25 Ma) to an extensional (25–8 Ma) regime. The occurrence of K-rich magmatism during the period 25–8 Ma is a consequence of the decompression melting of an enriched mantle source, which may signal the onset of extension in the southern Tibetan Plateau and provide a petrological record of the extension process.     

The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al₂O₃-FeO-Fe₂O₃-MgO-Na₂O-SiO₂-H₂O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f_O2(g) values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f_O2(g) exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.     

Origin of the pre-tropical storm Debby (2006) African easterly wave-mesoscale convective system

The origins of the pre-Debby (2006) mesoscale convective system (MCS) and African easterly wave (AEW) and their precursors were traced back to the southwest Arabian Peninsula, Asir Mountains (AS), and Ethiopian Highlands (EH) in the vicinity of the ITCZ using satellite imagery, GFS analysis data and ARW model. The sources of the convective cloud clusters and vorticity perturbations were attributed to the cyclonic convergence of northeasterly Shamal wind and the Somali jet, especially when the Mediterranean High shifted toward east and the Indian Ocean high strengthened and its associated Somali jet penetrated farther to the north. The cyclonic vorticity perturbations were strengthened by the vorticity stretching associated with convective cloud clusters in the genesis region—southwest Arabian Peninsula. A conceptual model was proposed to explain the genesis of convective cloud clusters and cyclonic vorticity perturbations preceding the pre-Debby (2006) AEW–MCS system.