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.     

Na2O solubility in CaO-MgO-SiO2 melts

The sodium solubility in silicate melts in the CaO-MgO-SiO₂ (CMS) system at 1400 °C has been measured by using a closed thermochemical reactor designed to control alkali metal activity. In this reactor, Na_(g) evaporation from a Na₂O-xSiO₂ melt imposes an alkali metal vapor pressure in equilibrium with the molten silicate samples. Because of equilibrium conditions in the reactor, the activity of sodium-metal oxide in the molten samples is the same as that of the source, i.e., aNa₂O_(sample) = aNa₂O_(source). This design also allows to determine the sodium oxide activity coefficient in the samples. Thirty-three different CMS compositions were studied. The results show that the amount of sodium entering from the gas phase (i.e., Na₂O solubility) is strongly sensitive to silica content of the melt and, to a lesser extent, the relative amounts of CaO and MgO. Despite the large range of tested melt compositions (0 < CaO and MgO < 40; 40 < SiO₂ < 100; in wt%), we found that Na₂O solubility is conveniently modeled as a linear function of the optical basicity (Λ) calculated on a Na-free basis melt composition. In our experiments, γNa₂O_(sample) ranges from 7 × 10⁻⁷ to 5 × 10⁻⁶, indicating a strongly non-ideal behavior of Na₂O solubility in the studied CMS melts (γNa₂O_(sample) ? 1). In addition to showing the effect of sodium on phase relationships in the CMS system, this Na₂O solubility study brings valuable new constraints on how melt structure controls the solubility of Na in the CMS silicate melts. Our results suggest that Na₂O addition causes depolymerization of the melt by preferential breaking of Si-O-Si bonds of the most polymerized tetrahedral sites, mainly Q⁴.     

Modelling the impact of tectonics,surface conditions and sea surface temperatures on Saharan and sub-Saharan climate evolution

Using an Atmospheric Global Circulation Model, we assess the relevance of selected atmospheric mechanisms for climate evolution of Saharan and sub-Saharan regions since the Miocene. First, we test the influence of the East-African Rift System uplift on atmospheric dynamics. Although the uplift played an important role in triggering East-African rainfall, no significant impact over central and western Africa has been detected. We also analyse the feedbacks of a giant lake on the climate of Chad basin. First results infer a negative feedback of the giant lake on the water balance, as convection is weakened by the cold water surface and as water evaporated from the lake does not feed the basin hydrological cycle. Lastly, we suggest that colder than present sea surface temperatures over the Gulf of Guinea reinforce the West-African monsoon, by enhancing the moisture advection engine via stronger thermal contrast between the ocean and the continent.     

3. Solar System Formation and Early Evolution: the First 100 Million Years

The solar system, as we know it today, is about 4.5 billion years old. It is widely believed that it was essentially completed 100 million years after the formation of the Sun, which itself took less than 1 million years, although the exact chronology remains highly uncertain. For instance: which, of the giant planets or the terrestrial planets, formed first, and how? How did they acquire their mass? What was the early evolution of the “primitive solar nebula” (solar nebula for short)? What is its relation with the circumstellar disks that are ubiquitous around young low-mass stars today? Is it possible to define a “time zero” (t ₀), the epoch of the formation of the solar system? Is the solar system exceptional or common? This astronomical chapter focuses on the early stages, which determine in large part the subsequent evolution of the proto-solar system. This evolution is logarithmic, being very fast initially, then gradually slowing down. The chapter is thus divided in three parts: (1) The first million years: the stellar era. The dominant phase is the formation of the Sun in a stellar cluster, via accretion of material from a circumstellar disk, itself fed by a progressively vanishing circumstellar envelope. (2) The first 10 million years: the disk era. The dominant phase is the evolution and progressive disappearance of circumstellar disks around evolved young stars; planets will start to form at this stage. Important constraints on the solar nebula and on planet formation are drawn from the most primitive objects in the solar system, i.e., meteorites. (3) The first 100 million years: the “telluric” era. This phase is dominated by terrestrial (rocky) planet formation and differentiation, and the appearance of oceans and atmospheres.     

Assessment of a new solution for tracking pebbles in rivers based on active RFID

Low‐frequency passive integrated transponders (PIT tags), are commonly used for monitoring pebble mobility in gravel‐bed rivers. Although early studies reported high recovery rates for PIT tags used in small streams, recovery rates in larger systems remain low, substantially limiting the possibilities for their use in such rivers. These low recovery rates are potentially due to missed detections caused by tag signal collision, burial in the sediment layer deeper than the maximum detection range and insufficient (but still exhausting) field effort to cover the concerned areas. A potential solution for addressing these problems is to use active ultra‐high frequency (a‐UHF) transponders as these have a greater detection range and anti‐collision protocols. In order to assess the potential of such transponders for pebble tracking in rivers, we used 433.92 MHz COIN‐ID and COIN‐HC models (ELA Innovation Company, Montpellier, France). We completed several tests to (i) characterize transponder detection ranges in the water and in saturated sediment and (ii) develop field protocols for locating tags by combining global positioning systems (GPS) sites and transponder received signal strength indication (RSSI) levels. The results showed that (i) the maximum detection ranges are about 2.4 m in the water column and more than 2.6 m in a column of saturated gravelly‐sandy sediment, (ii) RSSI spatial interpolation can be used to determine transponder position with good accuracy (< 1 m), (iii) the desired minimal level of accuracy can be adjusted depending on in‐field effort and signal impulse interval, (iv) the RSSI maximal value observed cannot yet be used to determine transponder burial depth because of the multipath propagation of radio frequencies and the semi‐directional emission of the tag signal. Copyright © 2017 John Wiley & Sons, Ltd.     

Methane-derived authigenic carbonates from active hydrocarbon seeps of the St. Lawrence Estuary,Canada

Nearly 2000 pockmarks with diameters ranging from a few tens of meters up to 700 m are present on the seafloor of the St. Lawrence Estuary in eastern Canada. Coring of some pockmarks resulted in the recovery of various-sized and shaped carbonate concretions in a predominantly silty mud matrix. Petrographic and geochemical data on four authigenic carbonate concretions are reported as well as data from shell material in the unconsolidated sediment. Video observations and echo-sounder images indicate that the sampled pockmarks are actively gas venting. The video images show significant look-alike microbial mats in areas where gas is venting. The carbonate concretions are primarily made up of carbonate cements with varying percentage of shell fragments, micrite particles and fine-grained clastics. Orthorhombic crystal morphology and diagenetic fabrics including isopachous layers and botryoids characterize the aragonite cement. Oxygen isotopes ratios for the cement crusts do not record any thermal anomaly at the site of precipitation with δ¹⁸O_VPDB ratios (+3‰) in equilibrium with cold (5 °C) deep marine waters, whereas significant negative δ¹³C_VPDB ratios (−9.9 to −33.5‰) for cement and shell material within concretions indicate that the carbonates largely derive from the microbial oxidation of methane. The δ¹³C_VPDB ratios of aragonite shells (−2.7 to −5.6‰) taken from unconsolidated sediments at some distance from the concretions/vents show variable dilution of HCO₃⁻ with negative δ¹³C_VPDB ratios derived from microbial oxidation of methane with isotopically normal (0‰) marine bicarbonate. These results are in agreement with other lines of evidence suggesting that pockmarks formed through the recent and still active release of gas from a reservoir within the Paleozoic sedimentary succession.     

Radio observations of NGC 2808 and other globular clusters: constraints on intermediate-mass black holes

We present the results of a deep radio observation of the globular cluster NGC 2808. We show that there are no sources detected within the core of the cluster, placing constraints on both the pulsar population of the cluster and the mass of a possible intermediate-mass black hole in NGC 2808. We compare the results for this cluster with other constraints on intermediate-mass black holes derived from accretion measures. With the exception of G1 in M 31 which has previously shown radio emission, even with considerably more conservative assumptions, only the clusters with the poorest of observational constraints are consistent with falling on the   M _BH–σ  relation. This result is interpreted in terms of the fundamental differences between galaxies and globular clusters.     

Eddy formation in the bays of Kamchatka and fluxes to the open ocean

Ocean Dynamics - The Eastern Kamchatka Current (EKC) is the western boundary current of the North Pacific subpolar gyre. Southeast of the Kamchatka Peninsula lies a large anticyclonic eddy, the...     

Eurocode 8-compatible synthetic time-series as input to dynamic analysis

Nonlinear dynamic analysis of existing or planned structures often requires the use of accelerograms that match a target design spectrum. Here, our main concern is to generate a set of motions with a good level of fit to the Eurocode 8 design spectra for France. Synthetic time series are generated by means of a non-stationary stochastic method. To calibrate the input parameters in the stochastic approach, we select a reference set of accelerograms for a Eurocode 8 type B site category from the PEER Ground-Motion Database, which are then adjusted to the target spectrum through wavelet addition. Then, we compute nonlinear seismic responses of a soil column, including pore pressure effects, and brittle and ductile structures to the stochastic time-series, the natural accelerograms and time-series generated using stationary stochastic approaches. The results of these calculations reveal considerable variability in response despite the similarities in terms of spectral acceleration.