Effects of temperature on the crystal structure of epidote: a neutron single-crystal diffraction study at 293 and 1,070 K

The effects of temperature on the crystal structure of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P2₁ /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe³⁺ at the M₃ site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe³⁺ share the M(3) site along with Al³⁺ [%Fe(M3)_1,070K = 74(2)%]. The refined amount of Fe³⁺ at the M(1) is not significant [%Fe(M1)_1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si₂O₇ group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe³⁺ between different octahedral sites and/or convergent ordering on M(3) are discussed.     

Generalized plasticity state parameter‐based model for saturated and unsaturated soils. Part 1: Saturated state

The behavior of granular materials is known to depend on its loose or dense nature, which in turns depends both on density and confining pressure. Many models developed in the past require the use of different sets of constitutive parameters for the same material under different confining pressures. The purpose of this paper is to extend a basic generalized plasticity model for sands proposed by Pastor, Zienkiewicz and Chan by modifying the main ingredients of the model flow—rule, loading–unloading discriminating direction and plastic modulus—to include a dependency on the state parameter. The proposed model is tested against the available experimental data on three different sands, using for each of them a single set of material parameters, finding a reasonably good agreement between experiments and predictions. Copyright © 2010 John Wiley & Sons, Ltd.     

Generalized plasticity state parameter‐based model for saturated and unsaturated soils. Part II: Unsaturated soil modeling

The aim of this paper is to extend the generalized plasticity state parameter‐based model presented in part 1 to reproduce the hydro‐mechanical behavior of unsaturated soils. The proposed model is based on two pairs of stress–strain variables and a suitable hardening law taking into account the bonding—debonding effect of suction and degree of saturation. A generalized state parameter for unsaturated state is proposed to reproduce soil behavior using a single set of material parameters. Generalized plasticity gives a suitable framework to reproduce not only monotonic stress path but also cyclic behavior. The hydraulic hysteresis during a drying—wetting cycle and the void ratio effect on the hydraulic behavior is introduced. Comparison between model simulations and a series of experimental data available, both cohesive and granular, are given to illustrate the accuracy of the enhanced generalized plasticity equation. Copyright © 2010 John Wiley & Sons, Ltd.     

Implications of Japan’s long term climate mitigation target and the relevance of uncertain nuclear policy

Achieving long-term climate mitigation goals in Japan faces several challenges, starting with the uncertain nuclear power policy after the 2011 earthquake, the uncertain availability and progress of energy technologies, as well as energy security concerns in light of a high dependency on fuel imports. The combined weight of these challenges needs to be clarified in terms of the energy system and macroeconomic impacts. We applied a general equilibrium energy economic model to assess these impacts on an 80% emission reduction target by 2050 considering several alternative scenarios for nuclear power deployment, technology availability, end use energy efficiency, and the price of fossil fuels. We found that achieving the mitigation target was feasible for all scenarios, with considerable reductions in total energy consumption (39%–50%), higher shares of low-carbon sources (43%–72% compared to 15%), and larger shares of electricity in the final energy supply (51%–58% compared to 42%). The economic impacts of limiting nuclear power by 2050 (3.5% GDP loss) were small compared to the lack of carbon capture and storage (CCS) (6.4% GDP loss). Mitigation scenarios led to an improvement in energy security indicators (trade dependency and diversity of primary energy sources) even in the absence of nuclear power. Moreover, preliminary analysis indicates that expanding the range of renewable energy resources can lower the macroeconomic impacts of the long term target considerably, and thus further in depth analysis is needed on this aspect.

Key policy insights

• For Japan, an emissions reduction target of 80% by 2050 is feasible without nuclear power or CCS.

• The macroeconomic impact of such a 2050 target was largest without CCS, and smallest without nuclear power.

• Energy security indicators improved in mitigation scenarios compared to the baseline.

     

Comparative Study of the Three-Dimensional Thermodynamical Structure of the Inner Corona of Solar Minimum Carrington Rotations 1915 and 2081

Using differential emission measure tomography (DEMT) based on time series of EUV images, we carry out a quantitative comparative analysis of the three-dimensional (3D) structure of the electron density and temperature of the inner corona (\(r<1.25\,\mathrm{R}_{\odot}\)) between two specific rotations selected from the last two solar minima, namely Carrington Rotations (CR)1915 and CR-2081. The analysis places error bars on the results because of the systematic uncertainty of the sources. While the results for CR-2081 are characterized by a remarkable north–south symmetry, the southern hemisphere for CR-1915 exhibits higher densities and temperatures than the northern hemisphere. The core region of the streamer belt in both rotations is found to be populated by structures whose temperature decreases with height (called “down loops” in our previous articles). They are characterized by plasma \(\beta\gtrsim1\), and may be the result of the efficient dissipation of Alfvén waves at low coronal heights. The comparative analysis reveals that the low latitudes of the equatorial streamer belt of CR-1915 exhibit higher densities than for CR-2081. This cannot be explained by the systematic uncertainties. In addition, the southern hemisphere of the streamer belt of CR-1915 is characterized by higher temperatures and density scale heights than for CR-2081. On the other hand, the coronal hole region of CR-1915 shows lower temperatures than for CR-2081. The reported differences are in the range \({\approx}\,10\,\mbox{--}\,25\%\), depending on the specific physical quantity and region that is compared, as fully detailed in the analysis. For other regions and/or physical quantities, the uncertainties do not allow assessing the thermodynamical differences between the two rotations. Future investigation will involve a DEMT analysis of other Carrington rotations selected from both epochs, and also a comparison of their tomographic reconstructions with magnetohydrodynamical simulations of the inner corona.     

Iron-hydroxide clogging of public supply wells receiving artificial recharge: near-well and in-well hydrological and hydrochemical observations

Clogging of water wells by iron-hydroxide incrustations due to mixing of anoxic and oxic groundwater is a common well-ageing problem. The relation between well operation (on and off), the spatial and temporal variations in hydrochemistry outside and inside a supply well, and the distribution of clogging iron-hydroxides were studied in an artificial recharge well field in the Netherlands. Camera inspection, high-resolution multi-level water sampling outside the well and detailed in-well pH/EC/O₂ profiles revealed remarkable patterns. During pumping, the top of the upper well screen abstracted oxic filtrate, although the larger part of the in-well water column was anoxic. The column rapidly turned oxic after shutdown due to a downward short-circuiting of oxic water via the well. Within 15 d it became anoxic due to the slow advance of anoxic lake filtrate created by local changes in flow direction as the neighboring wells continued to pump. Severe clogging occurred where the oxic filtrate entered the well, while half-clogging of the upper well screen occurred due to less inflow of oxic filtrate on the lake side. Transport of iron flocs and bacterial slimes after shutdown seemed to clog the lower part of the well screen. Frequent on/off switching should be avoided in iron-clogged wells.     

A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote

The effects of low-temperature on the crystal structure of a natural epidote [Ca_1.925Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P2₁ /m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe³⁺ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm⁻¹ are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe³⁺ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U _eq (defined as one-third of the trace of the orthogonalised U _ij tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U _eq of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%.     

Spatial and temporal variation of the nekton and hyperbenthos from a temperate European estuary with regulated freshwater inflow

The aquatic macrofauna of the Guadalquivir estuary were sampled (1 mm mesh persiana net) at 5 sampling sites located along the entire (except the tidal freshwater region) estuarine gradient of salinity (outer 50 km). A total of 134 fish and macroinvertebrate species was collected but only 62 were considered common or regularly present in the estuary. Univariate measures of the community structure showed statistically significant differences among sampling sites: species richness, abundance, and biomass decreased in the upstream direction, being positively correlated with the salinity. Temporal differences of these three variables were also statistically significant. While a clear seasonal pattern (minimum densities in winter and maximum in spring-summer) was observed for abundance and biomass, no such pattern existed for the number of species. Mysids was the most dominant group throughout the estuary (96% to 99% of abundance; 49% to 85% of biomass), although fish biomass was also important at the outer estuary (36% to 38%). Multivariate analyses indicated highly significant spatial variation in the macrofaunal communities observed along the salinity gradient. These analyses suggest that the underlying structure was a continuum with more or less overlapping distributions of the species dependent on their ability to tolerate different physicochemical conditions. There were also significant temporal (intermonthly + interannual) variation of the estuarine community; the relative multivariate dispersion indicated that monthly variation was more considerable (relative multivariate dispersion >1) at the outer part of the estuary during the wet year (last 20 km) and was higher in the inner stations during the dry year (32 to 50 km from the river mouth). Since a clear negative exponential relationship was observed between the freshwater input (from a dam located 110 km upstream) and water salinity at all sampling stations, it is concluded that the human freshwater management is probably affecting the studied estuarine communities. While the higher seasonal (long-term) stability of the salinity gradient, due to the human control of the freshwater input, may facilitate the recruitment of marine species juveniles during the meteorologically unstable early-spring, the additional (short-term) salinity fluctuations during the warm period may negatively affect species that complete their lifecycle within the estuary.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.