Thermal expansion and high temperature structure evolution of zoisite by single-crystal X-ray and neutron diffraction

The thermo-elastic behaviour and the temperature-induced structure evolution of a natural Fe-free zoisite have been investigated by in situ single-crystal X-ray and neutron diffraction. Neither discontinuities in volume expansion nor changes in symmetry have been observed up to 1,023 K. Zoisite shows a negative thermal expansion along [100] at T > 700 K, while a continuous positive expansion occurs on the (100) plane. Two different regimes in the anisotropic thermal behaviour of zoisite can be distinguished (i.e. at T < 700 K and T > 700 K), corresponding to an increase in the volumetric thermal expansion at T > 700 K. The structure evolution with temperature has been described by a series of X-ray and neutron refinements at different temperatures. In particular, the M(3) polyhedra show a significant octahedral flattening and expansion in the equatorial plane with T. All [SiO₄] tetrahedra show a regularization with increasing T. The neutron refinements show no change in the configuration of the hydrogen bonding at least up to 873 K. The effects of the T-induced main deformation mechanisms on the anisotropic elastic behaviour of zoisite are discussed. A comparison with the thermal behaviour of epidote has been carried out.     

Transgressive Eocene clastic–carbonate sediments from the Circum‐Rhodope belt,northeastern Greece: implications for a rocky shore palaeoenvironment

Locally exposed Middle to Upper Eocene conglomerates in the western part of the Cenozoic Thrace Basin are interpreted as products of continuous marine erosion of a rocky coast (consisting of Lower Cretaceous carbonates) and subsequent redeposition of the land‐derived limestone material in a wave‐dominated nearshore setting during a prolonged transgression. Contemporaneous biological activity in the warm‐temperate marine environment contributed to the accumulation of mixed coarse‐grained clastic–carbonate sediments on the upper shoreface. The formation of a relatively thick sedimentary succession was favoured by the interplay of several controlling factors as only shoreface deposits were preserved in the rock record. The results may help to elucidate the evolution of the hydrocarbon‐bearing Thrace Basin and to assist with the regional correlation of its basal deposits. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermo-elastic behaviour of Be2BO3OH (hambergite) up to 7 GPa and 1,100 K

The thermo-elastic behaviour of Be₂BO₃(OH)_0.96F_0.04 (i.e. natural hambergite, Z = 8, a = 9.7564(1), b = 12.1980(2), c = 4.4300(1) Å, V = 527.21(1) ų, space group Pbca) has been investigated up to 7 GPa (at 298 K) and up to 1,100 K (at 0.0001 GPa) by means of in situ single-crystal X-ray diffraction and synchrotron powder diffraction, respectively. No phase transition or anomalous elastic behaviour has been observed within the pressure range investigated. P?V data fitted to a third-order Birch–Murnaghan equation of state give: V ₀ = 528.89(4) ų, K _T0 = 67.0(4) GPa and K′ = 5.4(1). The evolution of the lattice parameters with pressure is significantly anisotropic, being: K _T0(a):K _T0(b):K _T0(c) = 1:1.13:3.67. The high-temperature experiment shows evidence of structure breakdown at T > 973 K, with a significant increase in the full-width-at-half-maximum of all the Bragg peaks and an anomalous increase in the background of the diffraction pattern. The diffraction pattern was indexable up to 1,098 K. No new crystalline phase was observed up to 1,270 K. The diffraction data collected at room-T after the high-temperature experiment showed that the crystallinity was irreversibly compromised. The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α ₀ + α ₁ T ^?1/2. The refined parameters for Be₂BO₃(OH)_0.96F_0.04 are: α ₀ = 7.1(1) × 10^?5 K^?1 and α ₁ = ?8.9(2) × 10^?4 K ^?1/2 for the unit-cell volume, α ₀(a) = 1.52(9) × 10^?5 K^?1 and α ₁(a) = ?1.4(2) × 10^?4 K ^?1/2 for the a-axis, α ₀(b) = 4.4(1) × 10^?5 K^?1 and α ₁(b) = ?5.9(3) × 10^?4 K ^?1/2 for the b-axis, α ₀(c) = 1.07(8) × 10^?5 K^?1 and α ₁(c) = ?1.5(2) × 10^?4 K ^?1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α ₀(a):α ₀(b):α ₀(c) = 1.42:4.11:1. The main deformation mechanisms in response to the applied temperature, based on Rietveld structure refinement, are discussed.     

Damage assessment of fortresses after the 2012 Emilia earthquake (Italy)

The medieval fortresses are a very common and distinctive type among the Emilian historical constructions and the earthquake of May 20 and 29, 2012 highlighted their high vulnerability. Starting from the analysis of the geometrical and constructive features, the interpretation of their seismic vulnerability has been based on an accurate damage assessment and supported by the numerical results of typical configurations. An abacus of recurring seismic damage mechanisms in fortresses has been proposed: it in particular concerns the towers and their interaction with the fortress perimeter walls. Moreover, the seismic response of the most important fortresses in the epicentral area has been described referring to their historical notes, the recent interventions and their influence on the seismic damage.     

High-pressure X-ray study of LiCrSi2O6 clinopyroxene and the general compressibility trends for Li-clinopyroxenes

High-pressure single-crystal X-ray diffraction measurements of synthetic LiCrSi₂O₆ clinopyroxene (with space group P2₁/c) were performed in a diamond-anvil cell up to 7.970 GPa. No phase transition has been observed within the pressure range investigated, but the elastic behavior at lower pressures (up to ~2.5 GPa) is affected by an anomalous softening due to the proximity of the phase transition to the HT-C2/c phase at 330 K and at ambient pressure. A third-order Birch–Murnaghan equation of state fitted to the compression data above 2.5 GPa yields a bulk modulus K _T0 = 93(2) GPa and its first derivative K′ = 8.8(6). The structural data measured up to 7.970 GPa confirm that the space group P2₁/c is maintained throughout the whole pressure range investigated. The atomic parameters, obtained from the integrated diffraction intensities, suggest that the Li coordination polyhedron changes its coordination number from 5 to 6 at 6–7 GPa by means of the approach of the bridging O atom, related to the increased kinking of the B tetrahedral chain. Furthermore, at higher pressures, the structural evolution of LiCrSi₂O₆ provides evidence in the variation of kinking angles and bond lengths of a potential phase transition above 8 GPa to the HP-C2/c space group. A comparison of the Li-clinopyroxenes (M1 = Cr, Al, Sc, Ga, Mg + Fe) previously investigated and our sample shows that their elastic behavior and structural mechanisms of compression are analogous.     

The distribution and utility of sea‐level indicators in Eurasian sub‐Arctic salt marshes (White Sea,Russia)

In support of efforts to reconstruct relative sea level (RSL), we investigated the utility of foraminifera, diatoms and bulk‐sediment geochemistry (δ¹³C, C:N and parameters measured by Rock‐Eval pyrolysis) as sea‐level indicators in Eurasian sub‐Arctic salt marshes. At three salt marshes (<15 km apart) in Dvina Bay (White Sea, Russia), we collected surface sediment samples along transects from subtidal to Taiga forest environments. Foraminifera at all sites formed bipartite assemblages, where elevations below mean high higher water (MHHW) were dominated by Miliammina spp. and elevations between MHHW and the highest occurrence of foraminifera were dominated by Jadammina macrescens and Balticammina pseudomacrescens. Five high‐diversity groups of diatoms were identified and they displayed pronounced variability amongst the study sites. Bulk‐sediment geochemistry recognized two groups (clastic‐dominated environments below MHHW and organic‐rich environments above MHHW). As one group included subtidal elevations and the other included supratidal elevations, we conclude that the measured geochemical parameters are not stand‐alone sea‐level indicators. Core JT2012 captured a regressive sediment succession of clastic, tidal‐flat sediment overlain by salt‐marsh organic silt and freshwater peat. The salt‐marsh sediment accumulated at 2804±52 years before present and preserved foraminifera (Jadammina macrescens and Balticammina pseudomacrescens) with good analogy to modern assemblages indicating that RSL was +2.60±0.47 m at this time. Diatoms confirm that marine influence decreased through time, but the lack of analogy between modern and core assemblages limited their utility as sea‐level indicators. Geochemical parameters also indicate a reduction in marine influence through time. We conclude that RSL reconstructions derived from salt‐marsh sediment preserved beneath Eurasian sub‐Arctic peatlands can provide valuable insight into the spatio‐temporal evolution of the Fennoscandian and Eurasian ice sheets.     

Mechanisms controlling seasonal mixed layer temperature and salinity in the Southwestern Tropical Indian Ocean

We use a heat- and salt-conserving ocean state estimation product to study the seasonal cycles of the mixed layer (ML) temperature (MLT) and salinity (MLS) balances over the southwestern tropical Indian Ocean (SWTIO) thermocline ridge (STR; 50°–75°E, 12°–5°S). For seasonal MLT, surface heat flux and ocean processes are both important. They tend to re-enforce each other during peak cooling (May–June) and warming (November) periods, but not during transition periods. The dominant ocean process is wind-driven vertical mixing. It is modulated by the variable strength of the monsoon winds (which affect the vertical diffusivity), and to a lesser extent by variability of thermocline depth (which influences the vertical stratification across the ML base). For example, thermocline shoaling in April–July alters the vertical stratification near the ML base; thus, when the monsoon winds heighten (June–September) and the vertical diffusivity increases (deepening the ML base), relatively cool subsurface water is near the ML base and easily incorporated into the ML by vertical mixing. However, vertical advection as a direct response to thermocline shoaling has little affect on MLT. This explains why MLT and thermocline depth are not positively correlated here on the seasonal timescale (as they are on the interannual timescale). Meridional advection associated with Ekman transport driven by the monsoon winds plays a secondary role. Seasonal MLS, however, is dominated by meridional advection. Vertical process effects on MLS are small, due to a weak salinity gradient near the ML base throughout the year.     

Legal challenges to the management of transboundary watercourses in Central Asia under the conditions of Eurasian Economic Integration

Worldwide experience has shown that interstate economic integration can help states in strengthening of management of transboundary waters and international water law serves as a reference for developing of relevant interstate cooperation. Transboundary waters in Central Asia play important role in the economic cooperation among riparian states, including those who are members of the Eurasian Economic Union (EAEU). At the current stage of transboundary waters management in Central Asia, the obsolete legal status is evident. The international water law sources developed under the United Nations’ auspices have no binding application due to luck of formal membership of the EAEU states in these treaties. Also the regional set of regulations, especially for the Aral Sea Basin, needs further enhancement and more efficient implementation. The bilateral interstate regulatory framework of the managemennt of waters shared by EAEU states in Central Asia requires development of additional rules to enable better accommodation of challenges existing in terms of the current interstate cooperation. Having said that can one further assume that EAEU could serve as a new legal framework for more effective cooperation on transboundary watercourses in Central Asia? The answer might be yes, but… the current stage of the legal framework for cooperation on transboundary waters within the EAEU requires sufficient enhancements in terms of developing its legal and institutional framework. The first condition for EAEU to serve as framework for cooperation on transboundary waters of Central Asia is to strengthen the regulatory framework for the cooperation of EAEU member states regarding environmental issues in general and transboundary water relations in particular, able to accommodate two main goals: environmental protection on the one hand and economic development on the other hand. The EAEU legal framework shall also lead to improvement of existing institutional cooperation and a dispute settlement mechanism on transboundary waters shared by the member states of the EAEU.     

Array analyses of volcanic earthquakes and tremor recorded at Las Cañadas caldera (Tenerife Island, Spain) during the 2004 seismic activation of Teide volcano

We analyze data from three seismic antennas deployed in Las Cañadas caldera (Tenerife) during May–July 2004. The period selected for the analysis (May 12–31, 2004) constitutes one of the most active seismic episodes reported in the area, except for the precursory seismicity accompanying historical eruptions. Most seismic signals recorded by the antennas were volcano-tectonic (VT) earthquakes. They usually exhibited low magnitudes, although some of them were large enough to be felt at nearby villages. A few long-period (LP) events, generally associated with the presence of volcanic fluids in the medium, were also detected. Furthermore, we detected the appearance of a continuous tremor that started on May 18 and lasted for several weeks, at least until the end of the recording period. It is the first time that volcanic tremor has been reported at Teide volcano. This tremor was a small-amplitude, narrow-band signal with central frequency in the range 1–6 Hz. It was detected at the three antennas located in Las Cañadas caldera. We applied the zero-lag cross-correlation (ZLCC) method to estimate the propagation parameters (back-azimuth and apparent slowness) of the recorded signals. For VT earthquakes, we also determined the S–P times and source locations. Our results indicate that at the beginning of the analyzed period most earthquakes clustered in a deep volume below the northwest flank of Teide volcano. The similarity of the propagation parameters obtained for LP events and these early VT earthquakes suggests that LP events might also originate within the source volume of the VT cluster. During the last two weeks of May, VT earthquakes were generally shallower, and spread all over Las Cañadas caldera. Finally, the analysis of the tremor wavefield points to the presence of multiple, low-energy sources acting simultaneously. We propose a model to explain the pattern of seismicity observed at Teide volcano. The process started in early April with a deep magma injection under the northwest flank of Teide volcano, related to a basaltic magma chamber inferred by geological and geophysical studies. The stress changes associated with the injection produced the deep VT cluster. In turn, the occurrence of earthquakes permitted an enhanced supply of fresh magmatic gases toward the surface. This gas flow induced the generation of LP events. The gases permeated the volcanic edifice, producing lubrication of pre-existing fractures and thus favoring the occurrence of VT earthquakes. On May 18, the flow front reached the shallow aquifer located under Las Cañadas caldera. The induced instability constituted the driving mechanism of the observed tremor.