Micro-spectroscopic investigations of highly heterogeneous waste repository materials

Assuring safe disposal and long-term storage of radioactive and toxic wastes corresponds to a primary environmental task of present societies. To improve any technical limitation, a mechanistic understanding of the processes governing the binding of heavy metals and radionuclides is required. In this study, the significance of synchrotron-based X-ray microprobes for elucidating the spatial distribution and the speciation of radionuclides in highly heterogeneous waste repository materials will be outlined. A case study on the uptake process of Co in cementitious engineered barrier materials exposed to microbial degradation will be presented.     

Characterization of cristobalite in ash and dome rock from the Soufriere Hills volcano, Montserrat： Implications for respiratory health hazards

A link between the inhalation of respirable silicas （SiO2） and respiratory diseases such as silicosis is widely recognized. Ash from dome collapse eruptions on Montserrat has been found to contain high levels （〉20%） of silicas in the form of cristobalite, tridymite, quartz and/or amorphous silica. The toxicity of these silica polymorphs varies widely. Cristobalite and quartz （tridymite less well established） are viewed as carcinogenic to humans whereas amorphous silica generally shows a reduced biological response. In assessing the potential health effects of volcanic ash particulates it is vital to determine the types and concentration of silicas as well as their size （respirable fraction）, shape and surface properties. The aim of this study is to develop methods to assess potentially toxic respirable airborne silicas in the dome collapse ash （applicable to a range of ash types） and to develop a model to predict the levels and types of respirable silicas from future eruptions. The model is being developed by comparing dome rock with related ash from a series of previous eruption events. Mineralogical assessment using conventional scanning X-ray diffraction （XRD） was hampered by difficulties in differentiating characteristic peaks for cristobalite and tridymite in complex multi-component ash samples （containing high levels of plagioclase）. These difficulties have been largely overcome using an Enraf-Nonius PDS120 diffractometer with curved （120 degrees 20） position sensitive detector （PSD）. The determination of size, shape and elemental characteristics of ash particulate and dome rock samples has been carried out using automated analytical scanning electron microscopy. The quantification of mineral proportions using PSD-XRD was highly successful with an accuracy of 1 to 2 wt%. However, the determination of phase proportions using automated analytical SEM was problematic due to scattering effects and the multiphase nature of many of the particles.     

In situ time resolved synchrotron powder diffraction study of thaumasite

Structural changes during dehydration and subsequent decomposition in thaumasite Ca₃Si(SO₄)(CO₃)(OH)₆·12 H₂O were studied by in situ synchrotron powder diffraction between 303 and 1,098 K. Evolution of the crystal structure was observed through 28 structure refinements, by full profile Rietveld analysis performed in the P6₃ space group, between 300 and 417 K, whereupon the thaumasite structure was observed to breakdown. Within this temperature range, the cell parameters of thaumasite increased as a function of temperature in a nearly linear fashion up to about 393 K, at which temperature, a slight slope change was observed. Above 400 K, the thermogravimetric analysis revealed that the dehydration process proceeded very rapidly while the refined occupancy of water molecules dropped below a critical level, leading to instability in the thaumasite structure. At a same time, a remarkable change in the unit cell parameters occurring at about 417 K indicated that the crystal structure of thaumasite collapsed on losing the crystallization water and it turned amorphous. This result indicated that the dehydration/decomposition of thaumasite was induced by the departure of the crystallization water. At about 950 K, anhydrite and cristobalite crystallized from the thaumasite glass.     

Alteration, evaluation and use of extremaduran granite residues

The necessity of eliminating debris from a granite quarry has awakened an interest in applications of by-products, called “marginal arids”, in different fields, like construction and foundations for roadways, restoration, material for the manufacture of artificial rocks, and artesian products etc. Conclusions obtained from the results of tests carried out by X-ray diffraction of granite quarry by-products in Extremadura, Spain, submitted to different treatments, are established. Test pieces from two quarries are analyzed and compared generally and specifically, for commercial use. Finally, conclusions relating to essays in test pieces and mineral dynamics of marginal arid granite are exposed.     

The effect of composition and cation ordering on the compressibility of columbites up to 7 GPa

The unit-cell parameters of two columbite samples along the (Fe,Mn)Nb₂O₆ solid solution were measured by means of high-pressure single-crystal X-ray diffraction up to pressures of 7 GPa. The compressional behaviour of these minerals was studied as a function of composition and degree of order. The P–V data of all the samples were fitted with a third-order Birch–Murnaghan equation of state. For the two samples with different compositions but identical degree of order the substitution of Mn for Fe causes a decrease of the bulk modulus K _T0, from 153(1) to 146(1) GPa, without any effect on the pressure first derivative K′. For the two samples with the same composition, cation ordering causes an increase of the bulk modulus from 149(1) to 153(1) GPa and of the pressure first derivative from 4.1(2) to 4.8(3). The compressional behaviour is anisotropic with a linear axial compressibility scheme β _b > β _c ≥ β _a for all samples, regardless of composition and degree of order. Such anisotropy increases sligthly with increasing Mn content.     

微量相X射线衍射定量分析的一种简便方法

阐述了关于微量相X射线衍射定量分析的一种简便方法———近似线性关系法,它适用于二相体系(或基体吸收系数基本恒定的多相体系)材料中微量相的定量分析。该方法不需要在待测样品中加入参考物相,分析时仅需对一条衍射线进行测定,因而分析时间很短,其测定结果与实际含量的相对误差为-10.2%～ 21.4%,与外标法和内标法的测量结果的精度相当。     

理学3080E3型X射线荧光光谱仪维修实例

介绍理学3080E3型X射线荧光光谱仪样品驱动单元及高压发生器部分的故障现象及维修实例。     

喉癌CT分型和CD44V6表达的意义

目的 探讨喉癌的CT分型和转移相关因子CD44V6表达的意义。方法 对39例喉鳞癌行术前常规CT检查，其术后标本进行CD44V6的表达检测，与术前CT片作对照分析。结果39例喉鳞癌CT检查；声门型24例，声门上型14例，跨声门型1例，声门下型0例；T1－2级22例，T3－4级17例；淋巴结转移组13例，非转移组26例，CD44V6总的阳性表达率为61．5％，对各组均采用秩次检验分析，CD44V6在喉癌的CT的T分级和淋巴结分组中存在显著性差异（P＜0．01）。而部位分区无明显差异。结论 喉癌的CT分型中的T分级、淋巴结分组与CD44V6的阳性表达密切相关。     

ARL9400型X荧光光谱仪探测器高压部分故障分析与维修

简述了瑞士ARL 9400型X荧光光谱仪探测器高压部分的故障现象、分析与处理及维修方法，并给出了维修实例。     

Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal

 A Raman scattering and X-ray diffraction study of the thermal decomposition of a naturally occurring, ettringite-group crystal is presented. Raman spectra, recorded with increasing temperature, indicate that the thermal decomposition begins at ≈55 °C, accompanied by dehydration of water molecules from the mineral. This is in contrast to previous studies that reported higher temperature breakdown of ettringite. The dehydration is completed by 175 °C and this results in total collapse of the crystalline structure and the material becomes amorphous. The Raman scattering results are supported by X-ray diffraction results obtained at increasing temperatures. Received: 9 July 2001 / Accepted: 14 August 2002