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.     

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

A neutron diffraction study of alkali cation migration in montmorillonites

Neutron powder diffraction measurements on lithium and cesium saturated montmorillonite samples before and after heat treatment at 300°C are studied, in order to undertake a complete refinement of crystal structure and unravel the migration mechanism for the interlayer cations of Li or Cs. Rietveld analysis of the corresponding diffraction patterns finds that montmorillonite crystallizes in the C2/m space group with unit cell dimensions consistent with the size of the specific interlayer cation. We show that thermal treatment affects the two types of samples in a different way. This is with respect to their unit cell dimensions and the migration of Li from the 2b to the 2c clay lattice site, in constrast to the Cs positioning which remains effectively unchanged.     

Comparative analyses of East Texas forest cover maps generated from Landsat and AVHRR data

Comparing satellite data derived map products are affected by differences in data characteristics, image acquisition dates, processing techniques, and classification schemes used for assigning pixels to a thematic class. By comparing two forest maps generated from Landsat Enhanced Thematic Mapper Plus (ETM+) and Advanced Very High Resolution Radiometer (AVHRR) images acquired on the same day, and processed using identical classification scheme and methods these differences were minimized. The ETM+ derived map had higher classification accuracy values and more precise area estimates than the AVHRR derived map. In the ETM+ derived map, 87 of the 599 verification data were misclassified, whereas in the AVHRR derived map, 155 of the 469 verification data were misclassified. Detailed error analyses by land cover class revealed that a land use based definition of forest accounted for 74% (64 out of 87) and 57% (89 out of 155) of the classification errors in ETM+ and AVHRR derived maps, respectively.     

The spatial implications of the functional proximity deriving from air passenger flows between European metropolitan urban regions

Until recently the traditional spatial configuration of the European geography was based upon the core-periphery model. The ‘pentagon’, broadly defined as lying between London, Paris, Milan, Munich and Hamburg, was seen as the core area characterised by having the highest concentration of economic development in the European Union (EU), with the remainder of the European territory viewed as peripheral, albeit to varying degrees. In a number of cases such peripheral areas equated with clear regional disparities. The elaboration of the European Spatial Development Perspective (ESDP) (CEC, European spatial development perspective, towards balanced and sustainable development in the territory of the European Union, 1999) challenged this core-periphery model. European spatial planning policies, aimed at encouraging social and economic, and with ever increasing importance, territorial cohesion, seek amongst other aspects to encourage the development of a balanced and polycentric urban system. This paper adopts a network analysis approach to the analysis of air passenger flows between some 28 principal European metropolitan urban regions. The evaluation of these flows contributes to an enhanced comprehension of the spatial dynamics of the European metropolitan territory which goes beyond that deriving from the more standard analyses of the individual components of the urban system. Several indicators are used, deriving from gravitational modelling techniques, to analyse the complexity of the air passenger flows. A multidimensional scaling (MDS) technique is introduced in order to interpret and visualise the resulting spatial configuration and positioning of the different metropolitan centres within the conceptual European ‘space of air passenger flows’, thereby contrasting with the more traditional map-based geographical image of Europe, based upon Cartesian coordinates.

Comparative urbanization in Ghana and Kenya in time and space

There are few inter-African country urban analyses because of the continent’s enormous size and socioeconomic diversity, language barriers, and wide variations in national and regional urban research capacity. Nevertheless, comparative urban studies are critical in understanding contemporary African urbanization. In this comparative spatial and temporal analysis of Ghana and Kenya’s urbanization, we find that both countries are urbanizing rapidly and are faced with many common urban problems. Moreover, Ghana is more urbanized than Kenya and has a larger indigenous urban imprint and a more widely dispersed urban pattern. Besides their physiographic and population conditions, we trace these countries’ convergent and divergent urban trends to their shared but unique experiences of colonialism, nationalism and globalization.     

Numerical estimation of REV and permeability tensor for fractured rock masses by composite element method

The Monte Carlo method is used to generate parent stochastic discrete fracture network, from which a series of fractured rock samples of different sizes and orientations are extracted. The fracture network combined with a regular grid forms composite element mesh of the fractured rock sample, in which each composite element is composed of sub‐elements incised by fracture segments. The composite element method (CEM) for the seepage is implemented to obtain the nodal hydraulic potential as well as the seepage flow rates through the fractured rock samples. The application of CEM enables a large quantity of stochastic tests for the fractured rock samples because the pre‐process is facilitated greatly. By changing the sizes and orientations of the samples, the analysis of the seepage characteristics is realized to evaluate the variation of the permeability components, the existence of the permeability tensor and the representative element volume. The feasibility and effectiveness are illustrated in a numerical example. Copyright © 2008 John Wiley & Sons, Ltd.     

The effect of naturally acidified irrigation water on agricultural volcanic soils. The case of Asembagus, Java, Indonesia

Acid water from the Banyuputih river (pH  3.5) is used for the irrigation of agricultural land in the Asembagus coastal area (East Java, Indonesia), with harmful consequences for rice yields. The river water has an unusual composition which is caused by seepage from the acidic Kawah Ijen crater lake into the river. This unique irrigation setting allows the study of soil acidification in situ. This paper assesses the effects of volcanogenically contaminated irrigation water on the chemical properties of the agricultural soils.The changes in soil properties were evaluated by comparing samples taken from the topsoil and sub-soil (1–3 m depth) from areas irrigated with acid water and areas irrigated with neutral water. The field survey thus resulted in four soil categories. Bulk soil composition, organic matter content, moisture content and particle size distribution were determined. Reactive phases were quantified with the selective extractions 1 M KCl, 0.1 M Na-pyrophosphate and 0.2 M acid ammonium oxalate (AAO).By comparing the four soil categories it is shown that the use of the naturally polluted irrigation water has had a large influence on the chemical composition of the topsoil. The composition of the soil solution has changed over the entire investigated soil profile. Furthermore the acid irrigation water has strongly modified the composition of the reactive phases, extracted as KCl, pyrophosphate, and AAO extractable elements, and also the bulk soil composition has been significantly modified. Overall this has resulted in the net dissolution of some elements and the net precipitation of others. The changes in the reactive phases and bulk soil composition are only apparent in the topsoil (0–20 cm) but not in the deeper soil.     

Geostatistical estimation of chemical contamination in stream sediments: The case study of Vale das Gatas mine (northern Portugal)

Based on an environmental geochemistry case study carried out in the neighbourhood of a W–Sn abandoned mine, the pollution in stream sediments was modelled through a Global Contamination Index. Such an index permits one to summarize the combination of deleterious elements in a single variable, obtained by the projection of samples onto the first axis of a PCASD (Principal Components Analysis of Standardized Data) applied to the entire n × p matrix containing the available concentrations of p = 16 elements in the set of n = 220 collected samples.In order to provide a sound basis for a coherent planning of the remediation process which will be put in operation in the affected area, it is necessary to balance the costs of reclaiming with the probabilities of exceeding the upper limits accepted for concentrations of environmentally harmful elements in sediments. Given these limits, they are back-transformed in the index values, providing a practical threshold between ‘clean’ and ‘contaminated’ samples. On the other hand, the minimum dimension of the cell to be reclaimed is restrained by the selected remediation process to be applied in the affected area. Hence, to meet the constraints of such a remediation process, it is required to estimate the probabilities of exceeding the index threshold in technologically meaningful sub-areas. For this end, the Indicator Block Kriging technique was applied, producing a series of maps where sub-areas to be reclaimed can be spotted for different probability levels. These maps, on which the decision making remediation agency can rely for its cost-benefit analysis, take into account both the spatial structure of ‘clean’ vs. ‘contaminated’ samples and the constraints of the reclaiming process.     

Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.