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.     

From outwash to coastal systems in the Portneuf–Forestville deltaic complex (Québec North Shore): Anatomy of a forced regressive deglacial sequence

Deglacial sequences typically include backstepping grounding zone wedges and prevailing glaciomarine depositional facies. However, in coastal domains, deglacial sequences are dominated by depositional systems ranging from turbiditic to fluvial facies. Such deglacial sequences are strongly impacted by glacio‐isostatic rebound, the rate and amplitude of which commonly outpaces those of post‐glacial eustatic sea‐level rise. This results in a sustained relative sea‐level fall covering the entire depositional time interval. This paper examines a Late Quaternary, forced regressive, deglacial sequence located on the North Shore of the St. Lawrence Estuary (Portneuf Peninsula, Québec, Canada) and aims to decipher the main controls that governed its stratigraphic architecture. The forced regressive deglacial sequence forms a thick (>100 m) and extensive (>100 km²) multiphased deltaic complex emplaced after the retreat of the Laurentide Ice Sheet margin from the study area ca 12 500 years ago. The sedimentary succession is composed of ice‐contact, glaciomarine, turbiditic, deltaic, fluvial and coastal depositional units. A four‐stage development is recognized: (i) an early ice‐contact stage (esker, glaciomarine mud and outwash fan); (ii) an in‐valley progradational stage (fjord head or moraine‐dammed lacustrine deltas) fed by glacigenics; (iii) an open‐coast deltaic progradation, when proglacial depositional systems expanded beyond the valley outlets and merged together; and (iv) a final stage of river entrenchment and shallow marine reworking that affected the previously emplaced deltaic complex. Most of the sedimentary volume (10 to 15 km³) was emplaced during the three‐first stages over a ca 2 kyr interval. In spite of sustained high rates of relative sea‐level fall (50 to 30 mm·year^?1), delta plain accretion occurred up to the end of the proglacial open‐coast progradational stage. River entrenchment only occurred later, after a significant decrease in the relative sea‐level fall rates (<30 mm·year^?1), and was concurrent with the formation and preservation of extensive coastal deposits (raised beaches, spit platform and barrier sands). The turnaround from delta plain accretion to river entrenchment and coastal erosion is interpreted to be a consequence of the retreat of the ice margin from the river drainage basins that led to the drastic drop of sediment supply and the abrupt decrease in progradation rates. The main internal stratigraphic discontinuity within the forced regressive deglacial sequence does not reflect changes in relative sea‐level variations.     

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.     

Improving the simulation of fine-resolution landscape changes by coupling top-down and bottom-up land use and cover changes rules

Modelling land use and cover changes (LUCC) at local and landscape scales simultaneously, in terms of composition and configuration, remains today highly challenging. Agricultural landscapes offer an illustrative context for this purpose. This article presents a modelling platform (DYPAL) able to simulate LUCC at both local (agricultural parcel, farm) and landscape levels by combining LUCC processes with an optimization algorithm. The efficiency of this approach is assessed by comparing it with an approach applying the same LUCC processes without optimization. Simulations have been developed for two representative case studies of temperate intensive agricultural mosaics: (1) neutral landscapes with simple and theoretical rules and (2) observed landscapes with realistic crop successions rules. Results show that this modelling platform improves the simulation of LUCC achieved at fine resolution, although not systematically. Improvements are observed when compared to theoretical farming practices. But, when compared with an observed landscape, it is true for one type of (arable) farms only. Several hypotheses are discussed, such as the fact that farmers possibly do not follow optimized rules. Finally, this study illustrates that the use of several indices is crucial to assess whether a simulated landscape is realistic or not, because it does not rely to the assessment of the predictive power of the model.     

Climate variability and trends in downscaled high-resolution simulations and projections over Metropolitan France

In order to fulfill the society demand for climate information at the spatial scale allowing impact studies, long-term high-resolution climate simulations are produced, over an area covering metropolitan France. One of the major goals of this article is to investigate whether such simulations appropriately simulate the spatial and temporal variability of the current climate, using two simulation chains. These start from the global IPSL-CM4 climate model, using two regional models (LMDz and MM5) at moderate resolution (15–20 km), followed with a statistical downscaling method in order to reach a target resolution of 8 km. The statistical downscaling technique includes a non-parametric method that corrects the distribution by using high-resolution analyses over France. First the uncorrected simulations are evaluated against a set of high-resolution analyses, with a focus on temperature and precipitation. Uncorrected downscaled temperatures suffer from a cold bias that is present in the global model as well. Precipitations biases have a season- and model-dependent behavior. Dynamical models overestimate rainfall but with different patterns and amplitude, but both have underestimations in the South-Eastern area (Cevennes mountains) in winter. A variance decomposition shows that uncorrected simulations fairly well capture observed variances from inter-annual to high-frequency intra-seasonal time scales. After correction, distributions match with analyses by construction, but it is shown that spatial coherence, persistence properties of warm, cold and dry episodes also match to a certain extent. Another aim of the article is to describe the changes for future climate obtained using these simulations under Scenario A1B. Results are presented on the changes between current and mid-term future (2021–2050) averages and variability over France. Interestingly, even though the same global climate model is used at the boundaries, regional climate change responses from the two models significantly differ.     

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.     

Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na₂O₂) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g⁻¹). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.     

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.