Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides (⁵⁹Ni, ¹³⁵Cs) in vitrified nuclear waste.The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass.Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe₂O₄), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of trioctahedral Mg-clay minerals. Alternative models assuming other elements (Ni, Al, Fe) in addition to Mg in the second shell could not be fitted successfully.Aqueous concentration data were used to calculate the speciation of the leaching solutions. Saturation index (SI) calculations indicate undersaturation with respect to NiCO₃ and NiSO₄·7H₂O, but oversaturation with respect to β-Ni(OH)₂. The latter result is probably due to the omission of Ni borate and Ni silicate complexes in the speciation calculations, for which formation constants are not available. With the help of estimation techniques, we could infer that such complexes would dominate the Ni speciation and consequently reduce the SI below the saturation of β-Ni(OH)₂.The μ-XRF maps show that Cs is uniformly distributed in the MW glass, since no region with high Cs concentration could be detected. The Cs L_III-edge μ-XAS spectra were all very similar independently of the degree of alteration, indicating similar coordination environments of Cs in the core regions of the glass as well as in the secondary clays. These spectra largely differ from that measured for pollucite (a potential secondary Cs-phase in altered glasses) implying that the coordination environments of Cs in the MW glass and in pollucite are fundamentally different.The present study shows that μ-XRF and μ-XAS are essential tools in determining the fate and the retention mechanisms of radionuclides released from nuclear waste during aqueous alteration. Our spectroscopic analyses allowed us to exclude formation of specific Ni and Cs secondary solids (e.g. nepouite, β-Ni(OH)₂, pollucite) during the aqueous alteration. Ni and Cs are instead distributed as trace elements in the alteration phases formed by major elements during the leaching process. Our results imply that solid solution and/or adsorption equilibria, rather than pure phase solubility equilibria, are the adequate chemical models to determine Ni and Cs aqueous concentrations in performance assessments for radioactive waste repositories.     

Intracrystalline microstructures in alkali feldspars from fluid-deficient felsic granulites: a mineral chemical and TEM study

Samples of essentially “dry” high-pressure felsic granulites from the Bohemian Massif (Variscan belt of Central Europe) contain up to 2-mm-large perthitic alkali feldspars with several generations of plagioclase precipitates in an orthoclase-rich host. The first generation takes the form of lenses homogeneous in size, whereas the size of a second generation of very thin albite-rich precipitates is more variable with comparatively high aspect ratios. In the vicinity of large kyanite, garnet or quartz inclusions, the first generation of plagioclase precipitates is significantly less abundant, the microstructure is coarser than in the remainder of the perthitic grain and the host is a tweed orthoclase. The first generation of precipitates formed at around 850 °C during the high-pressure stage (16–18 kbar) of metamorphism. Primary exsolution was followed by primary coarsening of the plagioclase precipitates, which still took place at high temperatures (850–700 °C). The coarsening was pronounced due to the access of fluids in the outer portions of the perthitic alkali feldspar and in more internal regions around large inclusions. The second generation of albite-rich precipitates was formed at around 570 °C. TEM investigations revealed that the interfaces between the second-generation plagioclase lamellae and the orthoclase-rich host are coherent or semi-coherent. During late evolutionary stages of the perthite, albite linings were formed at phase boundaries, and the perthitic microstructure was partially replaced by irregularly shaped precipitates of pure albite with incoherent interfaces. The albitization occurred below 400 °C and was linked to fluid infiltration in the course of deuteric alteration. Based on size-distribution analysis, it is inferred that the precipitates of the first generation were most probably formed by spinodal decomposition, whereas the precipitates of the second generation rather were formed by nucleation and growth.     

Immobilization of Ni by Al-modified montmorillonite: A novel uptake mechanism

The sorption capacity of montmorillonite clay minerals for small cations, such as Ni²⁺, can be greatly enhanced by modifying the clay mineral with Al(III). In this study, the mechanisms of Ni uptake by Al-modified montmorillonite were studied using extended x-ray absorption fine structure (EXAFS) spectroscopy of powders and polarized EXAFS spectroscopy of self-supporting clay films to delineate the binding structure of Ni formed as a function of the reaction conditions. Analysis of powder EXAFS spectra of wet pastes, collected from Ni-treated Al-modified montmorillonites reacted at pH 5-8, 25°C or 80°C (to accelerate the reaction process), and reaction times ranging from 1 month to 9 yrs, showed that Ni was surrounded on average by 6 O atoms at a distance of 2.05 Å and 6 Al atoms at 3.01 Å, suggesting the incorporation of Ni into a gibbsite-like structure. Only at pH 8, Ni-containing precipitates were congruently formed. Polarized EXAFS spectroscopy of self-supporting Ni-reacted Al-modified montmorillonite clay films showed a pronounced angular dependency of the spectra of the Ni-doped gibbsite, indicating that the orientation of this Ni-doped gibbsite coincided with the layering of the montmorillonite. Data analysis suggested that Ni is included slightly above and below the vacant octahedral sites of the postulated interstitial gibbsite monolayer. This newly identified mechanism of metal uptake by Al-modified montmorillonite provides a large metal sorption capacity and, because the metal is included in a monolayer gibbsite or gibbsite “islands” formed in the interstitial space of the clay mineral, it potentially leads to a permanent sequestration of the metal from the environment.     

中国西部壳幔结构与动力学过程及其对资源环境的制约:"羚羊计划"研究进展

为系统、深入地研究中国西部盆(盆地)、山(山脉)、原(高原)的壳幔结构与深部动力学过程,2003年我们提出并领导实施了“羚羊计划”(ANTILOPE-Array Network of Tibetan International Lithospheric Observation and Probe Experiments),在青藏高原先后完成了羚羊-I(ANTILOPE-I)到羚羊-IV(ANTILOPE-IV)4条二维宽频带台阵剖面,而在青藏高原东西构造结则实施了羚羊-V和羚羊-VI两个三维宽频带台阵探测。另外,我们将前期在准噶尔盆地、天山造山带、塔里木盆地、阿尔金造山带和柴达木盆地开展的九条综合地球物理观测剖面也纳入羚羊计划的总体框架中来。 通过“羚羊计划”的实施,我们在中国西部(包括西北部的环青藏高原盆山体系以及西南部的青藏高原)取得了大量的、高质量的、综合的第一手观测数据,获得了中国西部盆、山、原精细的壳幔结构,系统地揭示了中国西部盆山原的深部地球动力学过程。主要结论总结如下:确定了准噶尔盆地基底的结构与属性,优化了盆地的基底构造格架;建立了天山造山带“层间插入削减”新的陆内造山模式,揭示了印欧碰撞在天山岩石圈缩短44%的去向以及由洋-陆俯冲到陆-陆碰撞俯冲的转换机制;揭示了塔里木盆地、阿尔金造山带和柴达木盆地的盆山接触关系;获得了塔里木盆地顺时针旋转的深部几何学、运动学和动力学证据;确定了青藏高原之下印度板块与欧亚板块的碰撞边界;发现目前的青藏高原由南部的印度板块、北部的欧亚板块和夹持于二者之间的巨型破碎区——西藏“板块”构成,首次确定了各自的岩石圈底边界;修正了高原变形的两个端员模型;建立了深部构造对地表地形的制约关系;系统地揭示了印度板块沿喜马拉雅造山带俯冲的水平距离与俯冲角度的变化规律与控制因素。 “羚羊计划”以其巨大的观测网络与综合地球物理探测技术,采用地球物理学、地质学、地球化学等不同学科相结合的分析方法,揭示了印度板块俯冲、西藏巨型破碎区发育、塔里木板块顺时针旋转、西部水汽通道提前关闭、中国西北部干旱、沙漠化提前这一深部结构、动力学过程及其对地表地形、油气资源和环境变化的制约关系,推动了青藏高原地球系统科学理论的发展。     

Meteorite finds by EUROMET near Frontier Mountain,North Victoria Land,Antarctica

Abstract— A team from EUROMET (a joint initiative of scientific institutions in Europe interested in meteorites) was sent for the first time to Antarctica in the 1990/91 season to undertake a systematic search for meteorites. The project was organised within the framework of the Italian Antarctic Program (Programma Nationale di Richerche in Antartide, PNRA). The search was carried out in the vicinity of Frontier Mountain (North Victoria Land) and 256 meteorite fragments were discovered, most of which were wind-blown across the blue-ice field to the NE of Frontier Mountain and finally caught in an ice depression about 5 km to the N. The larger meteorites which remained on the ice surface from which they were uncovered may have been transported down to the mountain edge where they have subsequently been destroyed or covered in debris. A search for meteorites at neighbouring Sequence Hills, where similar glaciological conditions as at Frontier Mountain exist, proved unsuccessful. At this location the surface of the blue ice in the valleys with suspected meteorite concentrations was covered by meltwater lakes.     

Evolution and composition of the lithospheric mantle underneath the western Arabian peninsula: constraints from Sr−Nd isotope systematics of mantle xenoliths

On the basis of their textures and mineral compositions spinel-peridotite xenoliths of the Cr-diopside group (group I) from Cenozoic volcanic fields of Arabia can be classified into different subtypes. Type IA is of lherzolitic to harzburgitic composition; mineral compositions are similar to those of group I mantle xenoliths from worldwide occurrences. Type IB xenoliths have lherzolitic to wehrlitic compositions; Mg/(Mg+Fe) ratios of the clinopyroxenes (0.862–0.916) and olivines (0.872–0.914) are similar too or slightly lower than those of typical IA minerals. Texturally, type IB xenoliths are distinguished from type IA rocks by the presence of intragranular spinel, intragranular relict Cr-pargasite, and subordinate intergranular Ba-phlogopite (11.1% BaO). The hydrous minerals in type IB xenoliths are interpreted to document an earlier metasomatism 1 which did not affect type IA lithospheric mantle. Subsequent recrystallization caused the partial replacement of Cr-pargasite in type IB materials and resulted in the formation of less hydrous mineral assemblages. Some of the type IA xenoliths are characterized by secondary intergranular amphibole which must have formed recently. The absence or presence of this intergranular amphibole is used to distinguish an anhydrous subtype IA1 from a hydrous subtype IA2. Type IB xenoliths may also contain secondary intergranular amphibole (similar to the one in subtype IA2) or they contain abundant formermelt patches now consisting of glass and phenocrysts of olivine, clinopyroxene, amphibole, and spinel. The secondary intergranular amphiboles and the former melt patches, both are interpreted as results of a second metasomatism (metasomatism 2). In their trace element and isotopic characteristics, type IA1 and type IA2 clinopyroxenes do not exhibit any systematic differences. Furthermore, type IA2 clinopyroxenes are in Sr isotopic disequilibrium with intergranular amphiboles. This suggests that type IA2 clinopyroxenes were not modified during the second metasomatism 2. All type IA clinopyroxenes have low Sr contents (100 ppm); most of them show Sm/Nd ratios higher than inferred for bulk earth. In their ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios, type IA clinopyroxenes exhibit a large spread from 0.70226–0.70376 and from 0.51375–0.51251, respectively. Highly variable Sr/Nd ratios (5.0–79.3) and variable T_UR and T_CHUR model age relationships require different evolutions of the respective mantle portions. Nevertheless, all but two type IA clinopyroxenes form a linear array in a Sm–Nd isochron diagram which probably can not be explained by mixing. If taken as an isochron the slope of the array corresponds to an age of around 700 Ma. The mean initial _Nd of 5.8±1.7 (1) is similar to values for juvenile Pan-African (i.e. 850–650 Ma old) crust of the Arabian-Nubian shield. It is suggested that type IA lithospheric mantle and the juvenile Pan-African crust are two counterparts fractionated from a common source during the earlier stages of the Pan-African. Type IB clinopyroxenes have high Sr contents (200 ppm), variable Sr/Nd ratios (9–111) and Sm/Nd ratios generally below that inferred for bulk earth, and show a small spread in their Sr and Nd isotopic compositions (0.70299–0.70318 and 0.51285–0.51278, respectively). In a Sm–Nd isochron diagram the data points form a linear, horizontal array indicating a close-to-zero age for the earlier metasomatism 1 and suggesting a close genetic relationship to mantle processes related to the formation of the Red Sea.     

Shock-induced formation of kyanite (Al<Subscript>2</Subscript>SiO<Subscript>5</Subscript>) from sillimanite within a dense metamorphic rock from the Ries crater (Germany)

A dense (~3.34 g cm^–3) garnet–sillimanite-rich metamorphic rock from the suevite breccia of the Ries impact crater was studied by scanning-electron microscopy and Raman microprobe spectroscopy. In the strongly shocked rock clast kyanite was formed from sillimanite under momentary high pressures of natural shock waves. Kyanite aggregates were found as thin (~0.3–2.0 m) seams along grain boundaries between, and fractures within, sillimanite grains. Within these seams kyanite c-axes are oriented perpendicular to original grain boundaries and fractures. In addition, larger (up to 10 m) isolated kyanite grains were rarely found within host sillimanite. Filamentary kyanite aggregates and isolated crystals typically show shrinkage cracks due to volume decrease (~10%). Locally, broad interstices between sillimanite crystals are filled with aluminosilicate glass containing a high volume fraction of sub-micrometer-sized euhedral crystals. The silica-rich glass suggests incongruent melting of sillimanite at local post-shock temperatures significantly higher than 1,300°C. The edges of adjacent sillimanite grains are thermally and chemically altered. The local generation of temperature spikes is attributed to strong shock wave interactions due to very high shock impedance contrasts.