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     

G. Diego Gatta  Nicola Rotiroti  Martin Fisch  Milen Kadiyski  Thomas Armbruster 《Physics and Chemistry of Minerals》2008,35(9):521-533

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.  相似文献   

A neutron diffraction study of alkali cation migration in montmorillonites     

D. Gournis  A. Lappas  M. A. Karakassides  D. Többens  A. Moukarika 《Physics and Chemistry of Minerals》2008,35(1):49-58

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.  相似文献   

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

Malcolm C. Burns  Josep Roca Cladera  Montserrat Moix Bergadà 《GeoJournal》2008,71(1):37-52

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.

Malcolm C. BurnsEmail:

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Biaxial test simulations using a packing of polygonal particles   总被引：1，自引：0，他引：1  

A. A. Peña  A. Lizcano  F. Alonso‐Marroquin  H. J. Herrmann 《国际地质力学数值与分析法杂志》2008,32(2):143-160

The mechanical response of cohesionless granular materials under monotonic loading is studied by performing molecular dynamic simulations. The diversity of shapes of soil grains is modelled by using randomly generated convex polygons as granular particles. Results of the biaxial test obtained for dense and loose media show that samples achieve the same void ratio at large strains independent of their initial density state. This limit state resembles the so‐called critical state of soil mechanics, except for some stress fluctuations, which remain for large deformations. These fluctuations are studied at the micro‐mechanical level, by following the evolution of the co‐ordination number, force chains and the fraction of the sliding contacts of the sample. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

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

A.M.D. van Rotterdam-Los  S.P. Vriend  M.J. van Bergen  P.F.M. van Gaans   《Journal of Geochemical Exploration》2008,96(1):53-68

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.  相似文献   

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

A.R. Salgueiro  P. Freire vila  H. Garcia Pereira  J.M. Santos Oliveira 《Journal of Geochemical Exploration》2008,98(1-2):15

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.  相似文献   

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

Päivi M. Heikkinen  Marja L. Räisänen 《Journal of Geochemical Exploration》2008

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.  相似文献   

利用MC-ICPMS对水样中硼同位素比值的测定   总被引：2，自引：0，他引：2  

吕苑苑  许荣华  赵平  谢烈文  李禾 《地球化学》2008,37(1):1-8

采用Amberlite IRA-743硼特效树脂进行水溶液中硼的分离,对洗脱液温度、体积以及树脂动态交换容量等进行了实验.它的动态交换容量为4.2 mg/g,在室温条件下,用5 mL 2%HNO3可定量从树脂柱上洗脱被吸附的硼.采用Neptune型MC-ICPMS进行硼同位素组成的测定,1 μg/g浓度的硼标准溶液获得放大的信号强度约为0.7V,硼的化学分离过程有效避免了质量歧视效应.实验结果表明,MC-ICPMS对硼存在严重的记忆效应,通过采用5%HNO3-(1%HNO3 0.1%HF)-H2O-20%NH3H2O-H2O的交替清洗方法,可在约1 h内消除硼的记忆效应.在最佳仪器条件下,对含有250 ng硼的水样,可以快速测定硼的同位素组成,占δ11B测定的绝对偏差为0.4‰-0.5‰(SD).  相似文献   

土壤酶对碘离子在土壤中吸附行为的影响   总被引：1，自引：0，他引：1  

吴世军  陈繁荣  程俊  杨永强  吕莹  康明亮 《地球化学》2008,37(1):37-44

以批式试验法研究了微生物、葡萄糖氧化酶、脲酶、纤维素酶及其催化底物葡萄糖、尿素和纤维素对Ⅰ-在土壤中吸附的影响,结果表明微生物能显著提高Ⅰ-吸附量,但葡萄糖氧化酶、脲酶、纤维素酶及葡萄糖、尿素和纤维素对Ⅰ-吸附并无促进作用.葡萄糖氧化酶及葡萄糖含量在小于100 mg/L时对Ⅰ-吸附无影响,1000 mg/L时与Ⅰ-呈竞争吸附;脲酶及尿素随浓度增大,对Ⅰ-吸附的抑制作用变得明显;1～1000 mg/L范围内,纤维素酶和纤维素对Ⅰ-吸附没有影响;但葡萄糖氧化酶和葡萄糖生成的中间产物可促进土壤对Ⅰ-的吸附.平衡液中溶解性有机碳(DOC)含量随时间增加而逐渐降低,有机质浓度越大,降低趋势越明显.  相似文献   

云南罗平中三叠世安尼期生物群的发现及其意义   总被引：15，自引：0，他引：15  

张启跃  周长勇  吕涛  谢韬  楼雄英  刘伟  孙媛媛  江新胜 《地质论评》2008,54(4):523-526

本文介绍了云南罗平地区新发现的罗平生物群的产出层位、生物面貌、保存特征、古地理位置及其研究意义。该生物群产于关岭组二段薄层泥晶灰岩中,地层对比和化石鉴定表明其时代为中三叠世安尼期,以鱼类为主,伴生有爬行类、两栖类（？）、棘皮动物、节肢动物（甲壳类、昆虫等）、双壳类、腹足类以及植物化石;化石保存完好,分布广泛,埋藏方式独特。罗平生物群无论在丰度、分异度及化石保存上都极为罕见和独特,对研究埋藏学、古生态学、古地理以及三叠纪海洋生物尤其是海生爬行类都具有极为重要的意义。  相似文献