Cathodoluminescence, electron microscopy, and Raman spectroscopy of experimentally shock-metamorphosed zircon

Thorough understanding of the shock metamorphic signatures of zircon could be the basis for the use of this mineral as a powerful tool for the study of old, deeply eroded, and metamorphically overprinted impact structures and formations. This study of the cathodoluminescence (CL) and Raman spectroscopic signatures of experimentally (20-60 GPa) shock-metamorphosed zircon single crystals contributes to the understanding of high-pressure microdeformation in zircon. For all samples, an inverse relationship between the brightness of the backscattered electron (BSE) signal and the corresponding cathodoluminescence intensity was observed. The unshocked sample shows crosscutting, irregular fractures. The 20 GPa sample displays some kind of mosaic texture of CL brighter and darker domains, but does not exhibit any shock metamorphic features in BSE or CL images. The 40 GPa sample shows a high density of lamellar features, which might be explained by the phase transformation between zircon- and scheelite-structure phases of zircon and resulting differences in the energy levels of the activator elements. The CL spectra of unshocked and shocked (20, 40, and 60 GPa) zircon samples are dominated by narrow emission lines and broad bands in the region of visible light and in the near-UV range. The emission lines result from rare earth element activators and the broad bands might be associated with lattice defects. Raman spectra revealed that the unshocked and 20 GPa samples represent zircon-structure material, whereas the 40 GPa sample yielded additional peaks with relatively high peak intensities, which are indicative of the presence of the scheelite-type high-pressure phase. The 60 GPa sample has a Raman signature that is similar to that of an amorphous phase, in contrast to the observations of an earlier TEM study that the crystalline scheelite-structure phase is stable at this shock pressure. The 60 GPa Raman signature cannot be explained at this stage. The results show a clear dependence of the CL and Raman properties of zircon on shock pressure, which confirm the possible usage of these methods as shock indicators.     

蓝硒铜矿的发现及其地质意义

本文对产自湖北省恩施市双河硒矿鱼塘坝矿段氧化带中的极其少见的富铜亚硒酸盐矿物——蓝硒铜矿进行了详细的矿物学特征研究.蓝硒铜矿呈蓝色或天蓝色,透明,玻璃光泽,柱状晶体,一般颗粒非常细小,粒径大多在20~100μm,个别可>200μm.分散状,偶见穿插状、放射状聚晶体分布在碳质硅质页岩或粘土化火山碎屑岩的岩石裂缝中或岩层表面.与蓝硒铜矿共生矿物主要为星染状黄铁矿、微晶石英、伊利石、白云石和硒铜蓝等.利用电子探针(EMPA)和背散射电子衍射仪(EBSD)分析的蓝硒铜矿的化学组分表明,仅含Cu,Se和O元素,成分单一,其中SeO244.355%~49.778%(平均值47.684%),CuO37.419%~41.354%(平均值39.479%).计算的化学分子式为:Cu5.35~6.5[SeO3]5·6.2~9.95H2O,属于富铜的蓝硒铜矿,实际晶体化学式为:Cu[SeO3]·2H2O.蓝硒铜矿在显微镜下呈菱形横切面,平行消光,显示出正交晶系的光学特征.本文首次对蓝硒铜矿单晶体进行了“原位”拉曼光谱的测试分析,获得了清晰的拉曼谱线,其主要位移谱线为3506cm-1、3182cm-1、2917cm-1、1600cm-1、1328cm-1、814cm-1、727cm-1、555cm-1、378cm-1、288cm-1.蓝硒铜矿的傅里叶红外光谱主要特征吸收峰则与Sathi-anandan等(1964)合成的化合物相类似.根据蓝硒铜矿的产出地质特征、矿物组合和成矿环境条件,笔者认为蓝硒铜矿的形成是由于风化和淋滤富集作用所致.     

A Raman Investigation on the Boron form Occurring in Salt Lake Brine during Evaporation

Boron resources are abundant in the Da Qaidam Salt Lake of the Qaidamu basin in China,which has generated significant attention due to the presence of polyborate species in brine from this lake. In this study,Raman spectroscopy was used to investigate the existing form of boron in brine during evaporation. MgO·2 B_2 O_3-H_2 O,MgO·2 B_2 O_3-MgCl_2-H_2 O,and MgO·2 B_2 O_3-MgSO_4~-H_2 O solutions were also studied to determine the influence of boron concentration,pH,and electrolytes on the borate speciation from brine. The mononborates B( OH)_3 and B( OH)_4~-were found to be the only forms present in natural salt lake brine. Brine evaporation promoted the formation of the polyborate anions B_3 O_3( OH)_4~-,B_5 O_6( OH)_4~-,and B_6 O_7( OH)_6~(2-)and also promoted the disappearance of the B( OH)_4~-ion from brine at boron concentrations of more than 11 g/L B_2 O_3. The pentaborate ion B_5 O_6( OH)_4~-was sensitive to the solution pH and appeared only at p H values less than 8. 0. Meanwhile,the hexaborate ion B_6 O_7( OH)_6~(2-)was observed to be more dependent on the electrolyte magnesium chloride due to its special properties,such as promoting boron accumulation,lowering solution pH,and also its strong affinity for water molecules,which were all beneficial for the polymerization of borate ions in brine. Interaction mechanisms between polyborate anions during evaporation are also proposed herein. ake; evaporation; polyborate species; interaction mechanism.     

Microstructure of NH4Cl-NH3-H2O system studied by ATR-FTIR, Raman and MD simulation

The solubilities of ammonium chloride in aqueous ammonia decreased first and then increased with increasing ammonia concentrations, but the mechanism of this phenomenon has not been clarified. In the present work, the ATR-FTIR and Raman spectroscopy were employed to investigate the corresponding mechanism. The spectra analysis was focused on the region between 2500 and 4000 cm-1. It was firstly discovered that the N-H???N hydrogen bonds between ammonium ions and ammonia molecule was mainly formed in the NH4Cl-NH3-H2O system with concentrations higher than 10% ammonia, but N-H???O hydrogen bonds between ammonium ions and water molecule took advantage in the system with lower ammonia concentrations. Correspondingly, the phenomena of hydrogen bonding redshift and blueshift was observed respectively compared in NH3?H2O solution. Moreover, the hydrogen bonding structure of the saturated solution was obtained by means of MD simulation. The present work provides some theoretical basis for the separation of ammonium potassium chloride.     

Fourier transform infrared microspectroscopic characterization of Neoproterozoic organic microfossils from the Fifteenmile Group in Yukon,Canada

Conventional and synchrotron radiation‐based (SR) Fourier transform infrared microspectroscopies (micro‐FTIR) were applied to four types of ~ 810 Ma organic‐walled microfossils together with diffuse organic matter (OM) and one irregularly shaped structure from the Fifteenmile Group, in Yukon, Canada, for their chemical characterization. The microfossils comprised one filamentous type and three coccoidal types. Micro‐FTIR mapping analysis revealed the micrometer‐scale, spatial distribution of organic components (aliphatic C‐H bonds) and carbonate in the microfossils. Based on comparisons of CH₃/CH₂ peak height ratios (R_3/2) and morphologies of the microfossils (without the diffuse OM) to those of previously described Proterozoic microfossils, possible affinities of the microfossils are suggested, as follows. Palaeolyngbya? and Glenobotrydion belong to bacteria. Myxococcoides is not clearly characterized due to the significant mixing with diffuse OM containing abundant aliphatic C‐H groups. The irregularly shaped structure may represent a eukaryote. The diffuse OM may represent a mixture of decomposed microbial cells and extracellular polymeric substances (EPS). SR micro‐FTIR measurements of two coccoid types (Glenobotrydion and Unnamed Coccoid Form D) revealed that the R_3/2 values of the internal spots with wall structures are similar to those without wall structures in Glenobotrydion: those values from Unnamed Coccoid Form D were different. The results suggest that these two coccoids are different chemically as well as morphologically. Micro‐FTIR characterization of the organic‐walled microfossils together with morphological analysis provides new insight into their biological affinities.     

X射线粉晶衍射-拉曼光谱法研究含甲烷双组分水合物结构及谱学特征

天然气水合物的晶体结构主要取决于客体分子种类与组成,目前单组分水合物的结构和谱学特征较为明确,但多组分水合物相关研究较少.为解决多组分水合物的结构识别问题,探讨其谱学特征,本文实验合成了甲烷-丙烷(CH4-C3 H8)和甲烷-四氢呋喃(CH4-THF)两种含CH4双组分水合物以及CH4、C3 H8和THF等三种单组分水...     

福建煤系石墨资源状况和开发前景

福建省煤系石墨赋存于中二叠统童子岩组,是无烟煤受高温高压作用进一步变质而成,属隐晶质石墨。通过调查发现,福建省煤系石墨矿井、勘查区处于未开采或停采状态,开采矿区也多以煤炭开采的形式生产销售,造成资源浪费。为合理开发利用煤系石墨资源,采用d₀₀₂（碳层间距）-R₂（拉曼参数）模板鉴别煤系石墨并确定煤系石墨等级,结合区域构造的控制作用,划分了大田-漳平与永安-安溪石墨成矿区。在此基础上,综合实测数据和历年勘查资料分析,预测出永安长垇、永安下盖竹-甫弼-塘下洋、大田琼口-小溪洋-永安老鹰山、漳平可坑-乌石隔、漳平乌坑-华安福田5块煤系石墨资源远景区,其预测资源量8 196万t,展现了良好的开发前景。针对目前煤系石墨资源开发利用现状,提出“规范煤系石墨资源开采秩序、建立煤与煤系石墨鉴别指标并设立明确的煤矿与石墨矿权规范、优化石墨资源开发利用体系等”系列建议,以实现福建石墨产业结构协调化、技术高度化、产品系列化和价值链完整化。移动阅读      

Mineral fibres and environmental monitoring:A comparison of different analytical strategies in New Caledonia

Covered by ultrabasic units for more than a third of its surface,the New Caledonia(South West Pacific)is one of the largest world producers of Ni-ore from lateritic deposits.Almost all outcrops of geological units and open mines contain serpentine and amphibole,also as asbestos varieties.In this geological context,in which weathering processes had a great contribution in the production and dispersion of mineral fibres into the environment,the development of a routinely analytical strategy,able to discriminate an asbestiform fibre from a non-harmful particle,is a pivotal requisite.However,the acquisition of all these parameters is necessary for determining the risk associated to fibres exposition.A multidisciplinary routinely approach,based on the use of complementary simply-to-use but reliable analytical methods is the only possible strategy.In addition,the instrumental apparatus must be easily transportable on the field,directly on the mining site.The employment of specialized tools such as Polarized Light Microscopy associated to Dispersion Staining method(PLM/DS)and portable Raman spectroscopy for identification of environmental asbestos,are proved extremely effective in the improvement of the performance and rapidity of data acquisition and interpretation.Both PLM/DS and handheld Raman devices confirmed to be discriminant in the detection and characterization of asbestos fibres for both serpentine and amphibole.Furthermore,these techniques proved extremely effective even in the presence of strongly fibrous and altered samples.     

CH4-H2O体系流体包裹体拉曼光谱定量分析和计算方法

CH4—H2O体系流体包裹体研究对含油气盆地流体分析和成矿流体研究都有重要的意义。本文详细介绍了H2O、CH4和CH4—H2O体系的拉曼光谱特征及分子作用,分析了CH4—H2O体系热力学特征,同时对CH4—H2O体系流体包裹体拉曼光谱定量分析和计算的方法及步骤进行了叙述。利用人工合成流体包裹体建立甲烷浓度与拉曼特征峰面积比值之间的校正曲线是实现CH4—H2O体系流体包裹体定量分析的基础。盐度对包裹体定量分析的影响最为显著,在恒定甲烷浓度下,甲烷与水的拉曼峰面积比值随着盐度增加而减少。对于流体包裹体封闭体系,随温度升高,液相甲烷浓度增大。校正曲线必须包含对温度和盐度的校正。石英主矿物性质和方位对甲烷浓度定量分析的影响可以忽略。实验研究表明,原位拉曼光谱技术是准确获取流体包裹体中甲烷水合物生成条件的一种有效方法。因此,基于拉曼光谱分析和显微测温分析结果,采用热力学模型可以定量计算CH4—H2O体系流体包裹体的相关参数。