The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

The first record of a neonatal ornithopod dinosaur from Gondwana

Discrete post-embryonic teeth and bone fragments have been recovered from the matrix with the holotype skeleton (MPM‐10001) of the ornithopod dinosaur, Talenkauen santacrucensis Novas et al., 2004 (Upper Cretaceous, Argentina). The minute tooth crowns are 1 mm apicobasally tall and 1.7 mm mesodistally wide. The crowns are symmetrical and have a centrally located primary ridge on the lingual surface. Secondary ridges lead to five marginal denticles on both teeth. The tooth morphology is consistent with dentary teeth in euiguanodontids. There is no evidence of transport, suggesting that the material is autochthonous with respect to the adult body block of T. santacrucensis (MPM‐10001). Steeply inclined wear facets on the lingual surface and associated microstriae support the conclusion that the minute teeth were from a post-embryonic euiguanodontid dinosaur rather than early stage replacement teeth. The morphology, size, and wear of the teeth and small bone fragments found in the body block of MPM‐10001 suggest that this material belongs to a neonatal T. santacrucensis. This is the first record of neonatal ornithopod remains from Gondwana.     

Study of a rockfall in a limy conglomerate canyon (Covarrubias, Burgos, N. Spain)

In this paper, a rockfall of some tenths of cubic metres of rock, occurred in a conglomerate canyon in the northern Castilian plateau (N-Central Spain), is described in detail. This includes the basic data (geology, mapping, meteorological data and rock involved), the mechanical mechanism of the instability, the propagation and reach of the fallen rock boulders and the final location of the pieces. The study is based on detailed geological, aerial photography and geotechnical studies and advance topographical measurements. Geological engineering techniques are used to analyze the instability initiation and rockfall propagation. This study contributes to a better understanding of the geological processes leading to the occurrence of calcareous canyons and cliffs in the drainage network of the upper Castilian plateau. It is also helpful to improve our knowledge on natural rockfall phenomena for risk engineering purposes aiming to quantify, control and mitigate associated hazards.     

Late Variscan “Basin and Range” magmatism and tectonics in the Central Alps: evidence from U-Pb geochronology

Abstract

Towards the end of the Variscan orogeny, volcano-sedimentary basins were formed within the mountain hell. U-Pb age determinations on zircons of volcanic and plutonic rocks from intramontane basins of the Central Alps allows us to define the age of two volcano-sedimentary units: The former one was dated older than 333 Ma (probably Visean), the younger one was deposited in a short time span between 303 and 298 Ma (Stephanien). The latter contains tuffs (303 ± 4 Ma), ignimbrites and microgranites (299 ± 2 Ma) and intrusive rhyolites (300 ± 2 Ma) that are all coeval within analytical precision. Granitoid rocks intruded into the volcano-sedimentary rocks at 333 ± 2 Ma, 310 ± 3 Ma and 298 ± 2 Ma. An angular unconformity between the older and the younger units in the Tö di area (Aar massif) indicates uplift and erosion between 310 and 303 Ma.

Our results suggest the existence of two periods of late Variscan extension (or transtension) in the Alpine realm, both combined with magmatic activity. The extensional event of Stephaniun age is characterized by a short duration of only a few million years, between 303 and 298 Ma, comprising tectonic activity, volcanism and plutonism. The plutonic rocks are characterized by a dominant lithospheric mantle component, which was contaminated by different amounts of crostai material and might have been increasingly influenced by aslhcnos-pherie mantle melts in the course of crostai thinning. The ealc-alkaline geochemical characteristics of the granites may be explained as an inherited source feature.

The overall tectonic style and the mode of magmatism resembles the situation of the Basin-and-Kange Province (eastern USA). Consequently there is no need to invoke a late-Variscan Andean-type subduction to explain the geochemical composition of the magmatic rocks. We conclude that late-orogenic extension is an important tectonic stage of the Variscan orogeny, which lasted for some 50 million years. The extension led to thinning of the crust and upwelling of hot mantle, causing high heat flow, intrusion of mantle melts and formation of huge volumes of acid melts.     

Multi-stage evolution of a sub-aerial volcanic ridge over the last 1.3 Myr: S. Jorge Island, Azores Triple Junction

New K/Ar dating and geochemical analyses have been carried out on the WNW–ESE elongated oceanic island of S. Jorge to reconstruct the volcanic evolution of a linear ridge developed close to the Azores triple junction. We show that S. Jorge sub-aerial construction encompasses the last 1.3 Myr, a time interval far much longer than previously reported. The early development of the ridge involved a sub-aerial building phase exposed in the southeast end of the island and now constrained between 1.32 ± 0.02 and 1.21 ± 0.02 Ma. Basic lavas from this older stage are alkaline and enriched in incompatible elements, reflecting partial melting of an enriched mantle source. At least three differentiation cycles from alkaline basalts to mugearites are documented within this stage. The successive episodes of magma rising, storage and evolution suggest an intermittent re-opening of the magma feeding system, possibly due to recurrent tensional or trans-tensional tectonic events. Present data show a gap in sub-aerial volcanism before a second main ongoing building phase starting at about 750 ka. Sub-aerial construction of the S. Jorge ridge migrated progressively towards the west, but involved several overlapping volcanic episodes constrained along the main WNW–ESE structural axis of the island. Mafic magmas erupted during the second phase have been also generated by partial melting of an enriched mantle source. Trace element data suggest, however, variable and lower degrees of partial melting of a shallower mantle domain, which is interpreted as an increasing control of lithospheric deformation on the genesis and extraction of primitive melts during the last 750 kyr. The multi-stage development of the S. Jorge volcanic ridge over the last 1.3 Myr has most likely been greatly influenced by regional tectonics, controlled by deformation along the diffuse boundary between the Nubian and the Eurasian plates, and the increasing effect of sea-floor spreading at the Mid-Atlantic Ridge.     

Influence of Degree of Saturation in the Electric Resistivity–Hydraulic Conductivity Relationship

The relationship between aquifer hydraulic conductivity and aquifer resistivity, either measured on the ground surface by vertical electrical sounding (VES) or from resistivity logs, or measured in core samples have been published for different types of aquifers in different locations. Generally, these relationships are empirical and semi-empirical, and confined in few locations. This relation has a positive correlation in some studies and negative in others. So far, there is no potentially physical law controlling this relation, which is not completely understood. Electric current follows the path of least resistance, as does water. Within and around pores, the model of conduction of electricity is ionic and thus the resistivity of the medium is controlled more by porosity and water conductivity than by the resistivity of the rock matrix. Thus, at the pore level, the electrical path is similar to the hydraulic path and the resistivity should reflect hydraulic conductivity. We tried in this paper to study the effect of degree of groundwater saturation in the relation between hydraulic conductivity and bulk resistivity via a simple numerical analysis of Archie’s second law and a simplified Kozeny-Carmen equation. The study reached three characteristic non-linear relations between hydraulic conductivity and resistivity depending on the degree of saturation. These relations are: (1) An inverse power relation in fully saturated aquifers and when porosity equals water saturation, (2) An inverse polynomial relation in unsaturated aquifers, when water saturation is higher than 50%, higher than porosity, and (3) A direct polynomial relation in poorly saturated aquifers, when water saturation is lower than 50%, lower than porosity. These results are supported by some field scale relationships.     

Tides and mixing in the northwestern East China Sea Part I: Rotating and reversing tidal flows

Bottom-mounted ADV and ADCP instruments in combination with CTD profiling measurements taken along the Chinese coast of the East China Sea were used to study the vertical structure of temperature, salinity, and velocity in reversing tidal currents on a shallow inner shelf and in rotating tidal flows over a deeper sloping bottom of the outer shelf. These two regimes of barotropic tide affect small-scale dynamics in the lower part of the water column differently. The reversing flow was superimposed by seiches of ∼2.3 h period generated in semienclosed Jiaozhou Bay located nearby. As the tidal vector rotates over the sloping bottom, the height of the near-bottom logarithmic layer is subjected to tidal-induced variations. A maximum of horizontal velocity U_max appears at the upper boundary of the log layer during the first half of the current vector rotation from the minor to the major axis of tidal ellipse. In rotating tidal flow, vertical shear generated at the seafloor, propagated slowly to the water interior up to the height of U_max, with a phase speed of ∼5 m/h. The time-shifted shear inside the water column, relative to the shear at the bottom, was associated with periodically changing increases and decreases of the tidal velocity above the log layer toward the sea surface. In reversing flows, the shear generated near the bottom and the shear at the upper levels were almost in phase.     

Resting Stages of Plankton in Recent North Adriatic Sediments

Abstract. Plankton-derived resting stages were found in 26 sediment cores collected in the North Adriatic Sea; 46 morphotypes were identified, 38 were attributed to taxa according to their morphology and, in some hatching cases, also according to the morphology of the derived active forms. Six species of Dinophyta were recorded for the first time from the North Adriatic Sea. Each morphotype was described in detail. Twenty-nine resting stages were Dinophyta; one was a Chrysophyta; two were Tintinnina; and six were metazoans. At every site Dinophyta cysts were more abundant than Metazoa cysts. Cyst bank densities were variable, with empty forms generally more abundant than full ones; cyst concentrations were highest at the mouth of the Po River delta.     

An enhanced ensemble Kalman filter scheme incorporating model error in sequential coupling between flow and geomechanics

In this work, we construct a new methodology for enhancing the predictive accuracy of sequential methods for coupling flow and geomechanics while preserving low computational cost. The new computational approach is developed within the framework of the fixed-stress split algorithm procedure in conjunction with data assimilation based on the ensemble Kalman filter (EnKF). In this context, we identify the high-fidelity model with the two-way formulation where additional source term appears in the flow equation containing the time derivative of total mean stress. The iterative scheme is then interlaced with data assimilation steps, which also incorporate the modeling error inherent to the EnKF framework. Such a procedure gives rise to an “enhanced one-way formulation,” exhibiting substantial improvement in accuracy compared with the classical one-way method. The governing equations are discretized by mixed finite elements, and numerical simulation of a 2D slab problem between injection and production wells illustrate the tremendous achievement of the method proposed herein.