Na and HTO diffusion in compacted bentonite: Effect of surface chemistry and related texture

In underground repository concepts for radioactive waste, bentonite is studied as a reference swelling material to be used as an engineered barrier. Under the changing geochemical conditions prevailing within the barrier (saturation with the fluid coming from the host formation, diffusion of various chemical plumes caused by the degradation of some constituents of the barrier-system, etc.), the surface chemistry of the clay particles could evolve. This work aims to characterize the effects of these changes on (i) the microstructure of compacted bentonite samples and (ii) the diffusion properties of HTO and Na in these samples.For this purpose, bentonite sets were equilibrated with different solutions: NaCl, CaCl₂, CsCl solutions as well as an artificial clayey porewater solution. The microstructure of the different samples was characterized by HRTEM and XRD, in a water saturated state. In parallel, effective diffusion coefficients of both HTO and ²²Na were measured for the different samples. The density of the bentonite in the diffusion tests and in the HRTEM observations was set at 1.6 Mg m⁻³.From the microstructural observations and the results of diffusion tests, it is deduced that one key parameter is the occurrence of a gel phase in the material, which is found to depend strongly on the bentonite set: the gel phase dominates in Na-bentonite, while it is lacking in Cs-bentonite. The HTO diffusion coefficients are found to be lower in the samples with high gel phase content. Sodium diffusion does not follow the same trend: when compared with HTO, Na diffuses faster when the gel phase content is high. The latter result could indicate that the “accelerated diffusion mechanism” of cations, already mentioned in the literature, is enhanced in clayey materials that contain a gel phase.     

Climate change and community resilience in Samoa

Being resilient in the face of climate change seems especially important for island societies, which face the effects of rising temperatures, unpredictable rainfall, changing wind patterns and sea level rise. To date, most studies of adaptation and resilience among Pacific island communities have used indicators and methods rooted in Western science and neo-classical economics. These have been criticized as being locally irrelevant and inadequate to appreciate the dynamic nature and social structures of island communities and their capacity to adapt. This paper challenges the paradigm that defines resilience as a return to equilibrium, by using a non-equilibrium, cultural ecological lens. The non-equilibrium view of resilience sees the social systems of island nations as highly dynamic and undergoing persistent adaptation in the face of changing environmental factors. Field-based research undertaken in eight villages in Samoa found that, through constant exposure to environmental change over extended periods of time, communities have become resilient and are in a position to adapt to future changes. In developing future policy in relation to climate change, Pacific island governments need to develop a more nuanced understanding of islanders’ perceptions and historical actions in the context of both their physical locations and their dynamic socio-cultural systems.     

幔源云母巨晶氢同位素组成的微尺度不均一性:离子探针研究

运用离子探针技术对来自安徽女山新生代碧玄岩中的幔源云母巨晶进行了氢同位素组成的测定 ,发现其δD值和水含量存在微尺度不均一性 ,推断是与大气降水发生相互作用的结果 ;云母巨晶的原始δD值为 - 2 3‰ ,暗示其源区曾受到过再循环地壳的影响 ,同时也表明地幔氢同位素组成至少在大尺度上是不均一的 .     

Surface modes in the infrared spectrum of hydrous minerals: the OH stretching modes of bayerite

The theoretical infrared (IR) and Raman spectra of bayerite (β-Al(OH)₃) are computed in the density functional theory framework, using the linear response theory. The results are consistent with the occurrence of six non-equivalent OH groups in a bayerite structure with space group P2₁/n. Similar to gibbsite, the transmission powder IR spectrum of bayerite in the region of the OH stretching bands is found to depend on the shape of particles. In particular, the broadening of the strong band observed at about 3,460 cm⁻¹ in the spectrum of Al hydroxides is related to the electrostatic charges occurring at the surface of the polarized dielectric particles. The experimental correlation observed between the shape of this band and morphological parameters has therefore a physical, instead of chemical, origin.     

大陆岩石圈的流变学性质和矿物中的水

评述了近些年来岩石圈(尤其是大陆岩石圈)流变学研究中的主要进展。这些研究中最重要的一个发现是水的存在可以显著地增强岩石的变形,从而对其流变性质产生明显影响。大陆岩石圈的流变性质比大洋岩石圈要复杂得多,尤其是较深处的下地壳和岩石圈地幔之间流变性质的对比和差异成为近些年来人们争执较大的问题。大陆岩石圈的流变性质可能具有显著的不均一性,不仅体现在垂向上,也体现在横向上。根据流变学实验研究的进展和对深部壳幔捕虏体中主要构成矿物结构水含量的测定,对华北克拉通深部岩石圈的流变性质进行了定量计算。结果表明华北克拉通在重力梯度带两侧的岩石圈有着截然不同的流变特征,这种差异可能对两侧不同的岩石圈动力学过程有重要的影响。     

Spectroscopic investigation and theoretical modeling of kaolinite-group minerals and other low-temperature phases

This article summarizes some recent results obtained on the physical properties of environmental minerals, mostly kaolinite-group minerals and Fe- and Al-(hydr)oxides occurring in lateritic soils. The defective structure of these minerals, including impurities, stacking faults and radiation-induced defects, is probed using infrared spectroscopy and electron paramagnetic resonance. Resulting information bears on models of soil formation and transformation mechanisms of minerals in low-temperature environments. We underline the increasing impact of quantum chemical modeling in this field, providing straightforward interpretations of spectroscopic signals and overcoming the limits of fingerprint approaches. Importantly, the first-principles modeling of isotopic fractionation factors provides new links between mineralogical and geochemical investigations of secondary minerals.     

Numerical investigations of extreme winds over Switzerland during 1990–2010 winter storms with the Canadian Regional Climate Model

This study reports on the ability of the Canadian Regional Climate Model to simulate the surface wind gusts of 24 severe mid-latitude storms in Switzerland during the period 1990–2010. A multiple self-nesting approach is used, reaching a final 2-km grid which is centred over Switzerland, a country characterised by complex topography. A physically-based wind gust parameterization scheme is applied to simulate local surface gusts. Model performance is evaluated by comparing simulated wind speeds to time series at weather stations. While a number of simulated variables are reproduced in a realistic manner, the surface wind gusts show differences when compared to observed values. Results indicate that the performance of this parameterization scheme not only depends on the accuracy of the simulated planetary boundary layer, the vertical temperature, wind speed and atmospheric humidity profiles, but also on the accuracy of the reproduction of the surface fields such as temperature and moisture.     

Infrared spectroscopic properties of goethite: anharmonic broadening,long-range electrostatic effects and Al substitution

The infrared spectrum and its temperature dependence (20–320 K) were collected on a synthetic goethite sample (α-FeOOH). In addition, the infrared powder absorption spectrum of goethite and aluminum-substituted goethite was computed using ab initio quantum mechanical calculations based on density functional theory. This combined experimental and theoretical approach allows (1) the unequivocal assignment of absorption bands to the corresponding vibrational modes, (2) separate identification of the effects of the particle shape and of the aluminum substitution on the infrared spectrum, and (3) a discussion of the anharmonic properties and the origin of the line broadening in goethite. In particular, the two well-resolved OH bending absorption bands show different temperature evolution. Their detailed analysis suggests that the broadening of the band at ~800 cm^?1 cannot be described solely by a usual three-phonon process. The strong anharmonic behavior of this mode implies the addition of a four-phonon process, such as a pure dephasing process. In our calculations, the effect of the Hubbard U correction is also investigated and found to be most visible on the OH stretching and bending modes, in relation to the associated structural relaxation. The OH stretching frequencies decrease, leading to a better agreement with experimental frequencies, while the OH bending frequencies increase.     

Potential Orthopyroxene,Clinopyroxene and Olivine Reference Materials for In Situ Lithium Isotope Determination

Over 1400 electron probe and 700 ion probe microanalyses were performed on eleven mineral separates to evaluate their potential as reference materials for in situ Li isotopic determination. Our results suggest the homogenous distributions of major elements, Li and its isotopes for each sample. Hence, these samples are suitable to be used as reference materials for in situ measurements of Li abundance and Li isotopes by secondary ion mass spectrometry (SIMS) or laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). These samples have the advantage of mitigating probable matrix effects during calibration owing to the wide range of compositions. The effect of composition on the δ⁷Li of olivine measured by SIMS is a linear function of composition, with δ⁷Li increasing by 1.0‰ for each mole per cent decrease in forsterite component.