The structural role of Ti in aluminosilicate liquids in the glass transition range: insights from heat capacity and shear viscosity measurements

The shear viscosities and 1 bar heat capacities of glasses and melts along the 67mol% silica isopleth in the system SiO₂-Al₂O₃-Na₂O-TiO₂ have been determined in the temperature ranges 780-1140 K and 305-1090 K respectively. Anomalous behaviour of both these properties is observed for compositions rich in TiO₂ and/or Al₂O₃, an observation attributed to liquid-liquid phase separation followed by anatase crystallization. For samples which do not show anomalous behaviour, it is found that the partial molar heat capacity of the TiO₂ component previously determined in Al-free compositions reproduces our heat capacities to within 1.3%. Viscosity data show that addition of TiO₂ tends to increase viscosity and melt fragility at constant temperature. Furthermore, heat capacity and viscosity data may be combined within the framework of the Adam-Gibbs theory to extract values of the configurational entropy of the liquids and qualitative estimates of the variation of the average energy barrier to viscous flow. Configurational entropy at 900K is inferred to decrease upon addition of TiO₂, in contrast to previous results from Al-free systems. The compositional limit separating normal from anomalous behaviour, as well as the data for homogenous melts have been used to constrain the structural role of Ti in these samples. Our data are consistent with a majority of Ti in five-fold coordination associated with a titanyl bond, in agreement with previous spectroscopic studies. Furthermore, we find no evidence for a Ti-Al interaction in our samples, and we are led to the conclusion that Al and Ti are incompletely mixed, a hypothesis consistent with the observed reduction of configurational entropy upon addition of TiO₂, suggesting an important role of medium range order in controlling the variations in thermodynamic properties.     

Experimental determination of argon solubility in silicate melts: An assessment of the effects of liquid composition and temperature

The argon solubility of 38 liquids in the system Na₂O-CaO-MgO-Al₂O₃-SiO₂ (NCMAS) has been determined at 1873 K and 1 bar, the argon concentration of presaturated glasses being measured using a static mass spectrometer. For compositions in the subsystem diopside (CaMgSi₂O₆), nepheline (NaAlSiO₄), albite (NaAlSi₃O₈), anorthite (CaAl₂Si₂O₈), argon solubility is generally a linear function of the relative proportion of each end member, solubility being lowest in diopside melt (1.53 10⁻⁵ cm³ STP · g⁻¹ · bar⁻¹) and highest in albite melt (2.88 10⁻⁴ cm³ STP · g⁻¹ · bar⁻¹). For the tectosilicate joins studied (SiO₂-Na₂Al₂O₄, SiO₂-CaAl₂O₄, SiO₂-MgAl₂O₄) solubility decreases with decreasing silica content in all cases, being highest for Na-bearing liquids and lowest for Mg-bearing liquids at constant molar silica content. Where comparison is possible our results are in good agreement with data from the literature. When our data are considered in isolation we find that argon solubility shows an excellent correlation with calculated ionic porosity. The covariation of argon solubility and liquid density is also reasonable, that with molar volume less convincing and that with polymerization state (as defined by the ratio of the number of nonbridging oxygens and tetrahedral network forming cations; NBO/T) nonexistent. However, when our data are combined with those from the literature no well constrained correlation between argon solubility and ionic porosity is apparent. Based upon this observation and consideration of the temperature dependence of noble gas solubility it is concluded that ionic porosity is not a universally applicable parameter which may be used to predict noble gas solubility as a function of composition, temperature and pressure. Two new models for calculating argon solubility are proposed, both employing the notion of partial molar argon solubilities. The first uses oxide components, for which partial molar argon solubility is directly proportional to partial molar ionic porosity calculated at 1873 K, irrespective of the temperature of experimental equilibration. The second model, which offers the best fit to the available data, employs tetrahedral units rather than oxides as the proposed melt components. This latter model successfully accounts for reported argon solubilities in simple Al-free systems, in simple Al-bearing systems and in natural liquids. This is interpreted to infer that argon is incorporated in large sites in the liquid structure (such as the space within rings of n-tetrahedra) although further work is required to understand the quantitative links between melt structure and noble gas solubility.     

Dynamics and role of the Durban cyclonic eddy in the KwaZulu-Natal Bight ecosystem

The semi-permanent Durban Eddy is a mesoscale, lee-trapped, cold-core cyclonic circulation that occurs off the east coast of South Africa between Durban in the north and Sezela, some 70 km to the south. When present, strong north-eastward countercurrents reaching 100 cm s^–1 are found inshore. It is hypothesised that the cyclone is driven by the strong south-westward flowing Agulhas Current offshore of the regressing shelf edge near Durban. Analysis of ADCP data and satellite imagery shows the eddy to be present off Durban approximately 55% of the time, with an average lifespan of 8.6 days, and inter-eddy periods of 4 to 8 days. After spin-up the eddy breaks loose from its lee position and propagates downstream on the inshore boundary of the Agulhas Current. The eddy is highly variable in occurrence, strength and downstream propagation speeds. There is no detectable seasonal cycle in eddy occurrence, with the Natal Pulse causing more variability than any seasonal signal. A thermistor array deployed in the eddy centre, together with ship CTD data, indicates upward doming of the thermal structure in the eddy core associated with cooler water and nutrients being moved higher in the water column, stimulating primary production. Together with the use of satellite imagery, our findings indicate a second mechanism of upwelling, viz. divergent upwelling in the northern limb of the eddy. Satellite-tracked surface drifters released in the eddy demonstrated the potential for nutrient-rich eddy water to be transported northwards along the inshore regions of the KwaZulu-Natal (KZN) Bight, thus contributing to the functioning of the bight ecosystem, as well as southwards along the KZN and Transkei coasts – both by the eddy migrating downstream and by eddy water being recirculated into the inshore boundary of the Agulhas Current itself.     

Sharks caught in the KwaZulu-Natal bather protection programme,South Africa. 14. The smooth hammerhead shark Sphyrna zygaena (Linnaeus)

The current study provides long-term catch-rate, biological and feeding data for smooth hammerhead sharks, Sphyrna zygaena, caught in South Africa’s KwaZulu-Natal bather protection programme. In total, 2 512 S. zygaena were caught in net installations between 1978 and 2014, and 72 S. zygaena were caught on drumlines between 2007 and 2014. There was no significant log-linear year trend in the net catch rate over time (slope = 0.0054, t = 1.808, p = 0.07). However, there was a significant temporal increase in mean size of the captured sharks (slope = 0.0012, t = 3.502, p < 0.001). A quasi-Poisson generalised additive mixed model showed that increasing latitude, winter months, colder sea temperatures and the deployment of drumlines all had a significant positive effect on the catch rate of sharks in nets. The size frequency of the catch was unimodal, with significantly more females caught in the nets and more males on the drumlines. The majority (93.1%) of all sharks caught were immature and measured between 80 and 120 cm precaudal length. Teleosts and cephalopods dominated the sharks’ diet in terms of all dietary indices. The prey species consumed indicate that immature S. zygaena are feeding primarily within the pelagic zone of shallow coastal habitats.     

Carbonaceous chondrites as analogs for the composition and alteration of Ceres

The mineralogy and geochemistry of Ceres, as constrained by Dawn's instruments, are broadly consistent with a carbonaceous chondrite (CM/CI) bulk composition. Differences explainable by Ceres’s more advanced alteration include the formation of Mg‐rich serpentine and ammoniated clay; a greater proportion of carbonate and lesser organic matter; amounts of magnetite, sulfide, and carbon that could act as spectral darkening agents; and partial fractionation of water ice and silicates in the interior and regolith. Ceres is not spectrally unique, but is similar to a few other C‐class asteroids, which may also have suffered extensive alteration. All these bodies are among the largest carbonaceous chondrite asteroids, and they orbit in the same part of the Main Belt. Thus, the degree of alteration is apparently related to the size of the body. Although the ammonia now incorporated into clay likely condensed in the outer nebula, we cannot presently determine whether Ceres itself formed in the outer solar system and migrated inward or was assembled within the Main Belt, along with other carbonaceous chondrite bodies.     

Diet and gill morphology of the East Coast redeye round herring Etrumeus wongratanai off KwaZulu-Natal,South Africa

Stomach content analyses and measurements of gillraker morphology were used to assess the diet and feeding ecology of the East Coast redeye round herring Etrumeus wongratanai and provide data for comparisons with other small pelagic fishes off South Africa. Samples were collected by jigging from a kayak off Scottburgh, KwaZulu-Natal (KZN), over the period July 2013–May 2014. In total, 66 stomachs (containing 4 407 prey items) and 66 gill arches were examined. Stomach content analyses indicated that East Coast redeye round herring, at the time of sampling, fed on large (1 500–2 500?µm) particles, with ～2 500?µm particles making the greatest contribution to dietary carbon. The species feeds on larger particles than do anchovy Engraulis encrasicolus and sardine Sardinops sagax, but on particles of a similar size to those consumed by West Coast redeye round herring Etrumeus whiteheadi. There were significant differences in mean gillraker gaps between East Coast redeye round herring and both sardine and anchovy, but not between East Coast and West Coast redeye round herring. The differences in gillraker gaps between East Coast redeye round herring, sardine and anchovy are indicative of resource partitioning through differential feeding, based on zooplankton size. The data suggest that there is no resource partitioning between East and West coast redeye round herring, indicating that competition is likely to occur between them. However, such competition is minimised by limited spatial overlap between these two species.     

Highly reducing conditions during core formation on Mercury: Implications for internal structure and the origin of a magnetic field

The high average density and low surface FeO content of the planet Mercury are shown to be consistent with very low oxygen fugacity during core segregation, in the range 3-6 log units below the iron-wüstite buffer. These low oxygen fugacities, and associated high metal content, are characteristic of high-iron enstatite (EH) and Bencubbinite (CB) chondrites, raising the possibility that such materials may have been important building blocks for this planet. With this idea in mind we have explored the internal structure of a Mercury sized planet of EH or CB bulk composition. Phase equilibria in the silicate mantle have been modeled using the thermodynamic calculator p-MELTS, and these simulations suggest that orthopyroxene will be the dominant mantle phase for both EH and CB compositions, with crystalline SiO₂ being an important minor phase at all pressures. Simulations for both compositions predict a plagioclase-bearing “crust” at low pressure, significant clinopyroxene also being calculated for the CB bulk composition. Concerning the core, comparison with recent high pressure and high temperature experiments relevant to the formation of enstatite meteorites, suggest that the core of Mercury may contain several wt.% silicon, in addition to sulfur. In light of the pressure of the core-mantle boundary on Mercury (∼7 GPa) and the pressure at which the immiscibility gap in the system Fe-S-Si closes (∼15 GPa) we suggest that Mercury’s core may have a complex shell structure comprising: (i) an outer layer of Fe-S liquid, poor in Si; (ii) a middle layer of Fe-Si liquid, poor in S; and (iii) an inner core of solid metal. The distribution of heat-producing elements between mantle and core, and within a layered core have been quantified. Available data for Th and K suggest that these elements will not enter the core in significant amounts. On the other hand, for the case of U both recently published metal/silicate partitioning data, as well as observations of U distribution in enstatite chondrites, suggest that this element behaves as a chalcophile element at low oxygen fugacity. Using these new data we predict that U will be concentrated in the outer layer of the mercurian core. Heat from the decay of U could thus act to maintain this part of Mercury’s core molten, potentially contributing to the origin of Mercury’s magnetic field. This result contrasts with the Earth where the radioactive decay of U represents a negligible contribution to core heating.     

Equilibrium density and expansivity of silicate melts in the glass transition range

Equilibrium volumes and expansivities of three liquids in the system anorthite (CaAl₂Si₂O₈)–diopside (CaMgSi₂O₆) have been derived from dilatometric measurements of the equilibrium length of samples in the glass transition range. The typical temperature range of 40 K for the measurements is limited at low temperature by the very long times necessary to reach structural equilibrium and at high temperature by the penetration of the rod used to measure sample dilatation. Despite such narrow intervals, the expansivities are determined to better than 3% thanks to the high precision with which length changes are measured. The coefficient of volume thermal expansion (1/V dV/dT) of the fully relaxed liquid just above the glass transition is found to decrease linearly from diopside composition (139 ± 4 × 10⁻⁶ K⁻¹) to anorthite composition (59 ± 2 × 10⁻⁶ K⁻¹). These values are greater than those determined for the same liquids at superliquidus temperatures, demonstrating that expansivities of silicate melts may decrease markedly with increasing temperature. A predictive model based upon partial molar volumes which vary as a linear function of the logarithm of temperature is proposed. Received: 25 February 2000 / Accepted: 29 May 2000     

Plagioclase in the Skaergaard intrusion. Part 1: Core and rim compositions in the layered series

The anorthite content of plagioclase grains (X_An) in 12 rocks from the layered series of the Skaergaard intrusion has been studied by electron microprobe (typically ∼30 core and ∼70 rim analyses per thin section). Mean core compositions vary continuously from An₆₆ at the base of the layered series (LZa) to An_32–30 at the top. On the other hand, crystal rims are of approximately constant composition (An_{50 ± 1}) from the LZa to the lower Middle Zone (MZ). Above the MZ, core and rim compositions generally overlap. Profiles across individual plagioclase grains from the lower zone show that most crystals have an external zone buffered at X_An ∼50 ± 1. The simplest explanation for these features is that during postcumulus crystallization in the lower zone, interstitial liquids passed through a density maximum. This interpretation is consistent with proposed liquid lines of descent that predict silica enrichment of the liquid associated with the appearance of cumulus magnetite.