熔融制样X射线荧光光谱法测定含硫量高的石膏矿物中主次量元素

X射线荧光光谱法(XRF)已经应用于石膏等非金属矿物的测定,但由于石膏标准物质匮乏、硫含量较高且在高温易挥发损失,给测定带来了一定困难。本文采用石膏标准物质、高纯硫酸钙和其他国家一级标准物质(土壤、水系沉积物、碳酸盐)配制人工标准物质拟合校准曲线,优化稀释比、熔矿温度等熔融制样条件,用理论α系数校正基体效应,建立了采用XRF同时测定石膏矿中10个主次量元素(硅铝铁钙镁钾钠钛硫锶)的分析方法。样品与四硼酸锂-偏硼酸锂熔剂的稀释比为1∶9,在1050℃温度下样品熔融完全。方法检出限为4~135μg/g,精密度(RSD,n=12)小于3.0%。本方法配制的人工校准样品加强了样品基体的适应性,使用的四硼酸锂-偏硼酸锂熔剂在样品熔融过程中可有效地结合硫,抑制了硫的挥发损失,适用于批量分析硫含量高达12.60%~51.91%的实际石膏矿物。     

基于拉曼光谱-红外光谱-X射线衍射技术研究斜硅石的相对含量与石英质玉石结晶度的关系

石英质玉石的成分除α-石英外,还或多或少含有一种低温低压的SiO_2矿物"斜硅石",关于斜硅石的相对含量与石英质玉石结晶程度的关系还未见有研究。本文选取中国云南龙陵、安徽霍山、广西贺州和内蒙古阿拉善盟地区所产出的不同类型的石英质玉石为研究对象,采用拉曼光谱、红外光谱、X射线衍射分析技术,确定了斜硅石的相对含量与石英质玉石结晶程度之间的关系。结果表明,石英质玉石中斜硅石的相对含量越高,石英质玉石的结晶程度越低;其中拉曼光谱中能够描述斜硅石相对含量变化的502 cm~(-1)/465 cm~(-1)两峰强度比值(X)与石英质玉石的结晶度指数(Y)基本上呈负相关关系:Y=-0.36X+6.93(r=-0.94)。此结论为利用无损检测手段大致判断石英质玉石的结晶程度提供了新的思路,同时也为定性评价石英质玉石的品级提供了科学依据和理论约束。     

薄膜吸附制样-波长色散X射线荧光光谱法测定卤水中的溴

溴主要以离子形式分布在地壳水圈的溴化物型卤水、卤化物硫酸盐型卤水中,目前应用波长色散X射线荧光光谱(WDXRF)测定卤水中的溴,主要采用粉末载体压片法前处理待检样品,制样工作量大,制样均匀性和制样过程中的污染都会影响准确度,方法实用性不强。本文借助薄膜吸附前处理卤水样品,通过优化筛选薄膜材料及卤水取样量,确定移取50μL卤水样品滴于Ф=40 mm的3#层析滤纸的圆心位置,自然晾干后高压压平来前处理待检样品,采用人工配制标准样品校正溴的标准曲线,用WDXRF测定溴的含量。钾钠钙镁氯和硫酸根等共存离子的影响可以忽略,方法检出限(3σ)为0.95 mg/L,精密度(RSD,n=11)不大于0.8%,加标回收率为99.4%~101.2%。本方法操作简便,不需要使用化学试剂,解决了现行卤水中溴的分析方法流程复杂、分析成本高的问题。     

西藏曲水县达布斑岩型铜钼矿床金属沉淀机制探讨

西藏曲水县达布斑岩型铜钼矿床位于冈底斯成矿带中东段,其矿化体主要产于含矿斑岩体与围岩的内外接触带中。文章以矿石内Cu、Mo矿化石英脉中的流体包裹体为研究对象,探讨了成矿金属沉淀的机制。通过详细的显微镜下鉴定,发现Cu、Mo矿化阶段的流体包裹体类型均以L型为主,但Cu矿化阶段的V型包裹体明显较Mo矿化阶段多,而S型包裹体较少。Cu、Mo矿化石英脉中,常见L型、V型、S型流体包裹体共存的现象,且它们的均一温度范围非常接近,说明成矿流体经历了不混溶作用,使得高盐度流体与低密度气相流体发生分离。单个流体包裹体激光拉曼光谱测试显示,在Cu、Mo矿化阶段的气相包裹体中均检测到CO2的特征峰和H2O峰,而在Mo矿化阶段的气相包裹体仅检测到CH4特征峰,说明Mo矿化阶段的流体的相对还原性更强;同时,检测到硬石膏、赤铁矿、磁铁矿、黄铜矿、黄铁矿等子矿物,但硬石膏、赤铁矿、磁铁矿主要分布于Cu矿化阶段,说明Cu矿化阶段的流体氧化性相对较强。对单个流体包裹体进行同步辐射X射线荧光分析(SR-RXF)显示,Cu、Au等金属主要富集于流体包裹体气相中,表明Cu、Au元素可能是气相运移。对Cu、Mo硫化物沉淀的一系列化学反应研究表明,呈氧化态以及酸度低(HCl浓度低,即偏中性)的流体会促进黄铜矿饱和;活性较高的H2S和略呈还原性的流体有利于辉钼矿的沉淀。综合分析认为,铜矿化与偏中性、结晶分异程度相对较低的花岗闪长斑岩关系密切,而钼矿化与酸性、结晶分异程度相对较高的花岗斑岩关系密切。     

Cross-twinning in a natural spinel from Sri Lanka

A modified cross-twinning growth mechanism is put forward to explain the anomalous morphology of a spinel multiple-twin from Sri Lanka, flattened crosswise the twin planes. Cross-twinning in spinel was found also in other specimens from Pegu (Myanmar), and the results were published in a previous paper. This particular type of twinning is derived from the combination of cyclic twinning with lamellar twinning, so that these samples may be thought of as partial fivelings (cubic cyclic {111} twins with five components sharing a common <110> pseudo-fivefold axis). In the present paper, the sample from Sri Lanka has been suitably cut with the aim of focusing the study on the cross-twinning region. The transformation matrices that link the orientation states of each couple of twin components have been determined by means of White Beam Synchrotron Radiation Topography. They showed that the specimen is made up of four twin components (A, B, C and D), with three twin planes: and They also showed that the cross-twinned individuals (B and D) actually are not twinned to each other, and that a simple crystallographic relationship holds between them. X-ray diffraction topography by conventional source allowed to image the crossing-region and to determine that the cross-twinned individuals are in contact through a semi-coherent boundary, with twinning dislocations contributing to relieve the coherency strains. Electron probe microanalyses with wave dispersive spectroscopy showed that the chemical composition is almost homogeneous, at least within the spatial resolution limit of this technique. The similar growth features observed in the spinel sample from Sri Lanka and in those from Myanmar are interpreted as growth marks, indicators of a similar origin: in both cases they are found in impure dolomitic marbles. In particular, the specimen from Sri Lanka results from the interaction of thermal and metasomatic effects due to contact metamorphism. An unusual stepped morphology of the face close to the twin boundary, possibly due to corrosion and re-growth processes acted preferentially at a re-entrant corner by metasomatic fluids, is interpreted as indicator of a metasomatic event that succeeded to the crystal growth, the latter occurred by thermal effect.

Neutron diffraction study of aluminous hydroxide δ-AlOOD

We have determined the position of deuterium atoms in δ-AlOOD by neutron powder diffraction at ambient pressure. As previously reported by theoretical and experimental studies, the deuterium atoms are located in the tunnel formed by the chains of AlO₆ octahedra. The data are best fit with the P2₁ nm structure, producing bond lengths of D–O1 of 1.552(2) Å, O2–D of 1.020(2) Å and O1–O2 of 2.571(2). This study confirms that the hydrogen bond is asymmetric at ambient conditions in agreement with recent single-crystal synchrotron study for δ-AlOOH.     

基于气体吸附法和X射线Micro-CT三维成像技术定量解析天然和电化学处理绿松石孔隙特征

绿松石是一种多孔材料,其孔隙特征直接影响其颜色、光泽、硬度、耐久性等性质,进而影响其市场价值,电化学处理的主要目的是降低绿松石孔隙度从而使其耐久、保色。采用全自动比表面仪、X射线显微CT(Micro-CT)等测试分析手段,对电化学处理前后绿松石的孔隙特征进行了对比研究。比表面仪研究发现,电化学处理后的绿松石总孔隙度、总孔体积、平均孔径及比表面积均有一定程度的变化;吸附-脱附曲线高压区域天然绿松石吸附曲线斜率变大,而电化学处理绿松石吸附曲线斜率变小;天然绿松石孔径分布曲线为类抛物线,而电化学处理绿松石孔径分布曲线呈内凹曲线状。Micro-CT研究结果表明:天然绿松石中出现的由表面贯穿至内部的大孔洞,经电化学处理后孔洞被不完全充填;天然绿松石存在“流纹状”结构,孔隙沿“流纹”分布,而电化学处理绿松石的“流纹状”结构消失,孔隙分布杂乱无章。本研究首次从孔隙特征角度入手,发现天然绿松石与电化学处理绿松石在高压区域吸附曲线特征、50 nm孔径以上孔隙分布曲线、孔隙充填情况和内部结构等方面存在明显差异。通过检测绿松石的钾(K)含量,并结合孔隙特征差异,可以有效地对绿松石是否经过电化学处理进行检验判定。     

同步辐射加速器X荧光分析技术在极地环境研究中的应用

本文简要介绍了同步辐射器X荧光(SRXRF)技术的分析原理和特点。概述了该技术在极地环境研究中的应用,并对其发展前景进行了展望。     

弥漫性细支气管肺泡癌CT误诊分析(附15例报告)

目的:本文旨在提高对弥漫性细支气管肺泡癌的认识,及早诊断,减少误诊。方法:用CT机检查弥漫性细支气管肺泡癌15例的误诊,进行回顾性分析;结果:在所有被被误诊病例中,肺炎6例,肺结核7例,矽肺2例。结论:虽然弥漫性细支气管肺泡癌的早期表现缺乏特征表现,但加深对该病的认识及采取相关手段有助于该病的正确诊断。     

多层螺旋CT在乳腺疾病检查中的应用

目的探讨多层螺旋CT在乳腺疾病检查中的诊断价值。方法对29例患者行乳腺CT扫描,采用经容积再现(volumerendering,VR)、表面遮盖显示(surfaceshadowdisplay,SSD)、多平面重建(Multiplanar,MPR)重建处理图像。结果29例患者中乳腺癌12例,纤维瘤7例,均经病理证实,1例患者不能坚持俯卧而检查失败。结论多层螺旋CT对乳腺疾病的诊断有重要的参考价值。