An EFTEM/HRTEM high-resolution study of the near surface of labradorite feldspar altered at acid pH: evidence for interfacial dissolution-reprecipitation

Using an approach combining high-resolution and energy-filtered transmission electron microscopy (HRTEM and EFTEM), we have studied with Å to nm-spatial resolution the interfacial region that delimits the near-surface altered zone and non-altered labradorite feldspar after dissolution under acid pH conditions. The interface is characterized by extremely sharp and spatially coincident changes in structure and chemistry. The 500-nm-thick altered zone is depleted in interstitial cations (Ca, Na, K) and Al, a framework element, whereas it is enriched in H, O, and Si. Modeling H⁺-alkali interdiffusion within a 500-nm-thick altered zone shows that volume interdiffusion cannot reproduce the sharp chemical interfaces measured by EFTEM. Based on these new data, we propose that the near-surface altered zone is a result of interfacial dissolution-reprecipitation, and not of preferential leaching of cations and interdiffusion with H⁺. This implies an intrinsic dissolution process that is stoichiometric, where the breaking of bonds and release of interstitial cations and framework elements (Al, Si, and O) to solution occur contemporaneously at equal relative rates from the original fluid–mineral interface.     

Carbons at the heart of questions on energy and environment: A nanostructural approach

The organization of disordered carbons at the nanometer scale, or nanostructure, reveals very precisely their formation conditions, either in Nature or in the laboratory or in industry. Its study allows a better understanding of the properties of such solids. Only High-Resolution Transmission Electron Microscopy (HRTEM) allows a direct imaging of the nanostructure, whereas Raman microspectrometry provides quantitative but averaged structural data. Applications of the original coupling of Raman with HRTEM, especially in the fields of Energy and Environment, are numerous and promising. Two examples are given concerning the decontamination of irradiated nuclear graphite waste and detection of hydrocarbons trapped in oil and gas shales. Moreover, the study of wood carbonization led our team to propose a novel Raman-based paleothermometer. This approach finds an unexpected application in archeology (e.g., the study of fire marks in prehistoric caves).     

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

SAED and HRTEM Investigation of Palygorskite

The microstructure of palygorskite from Longwang Mountain of Xuyu County, Jiangsu Province, was studied by energy dispersive X-ray analysis （EDX）, selected-area electron diffraction （SAED） and high-resolution transmission electron microscopy （HRTEM）. The average composition of the palygorskite studied is （Si7.38A10.62） （A10.96Fe^3＋ 0.62Mg2.86 0.56）Ca0.03K0.06O20（OH）2（OH2）4, which is rich in Mg. Several SAED patterns from a single crystal of palygorskite were obtained with different zone axes. The polymorphs （monoclinic and orthorhombic） are unequivocally distinguished by distant interplanar angles, even though they possess similar sets of d-values. High-resolution images of three principal zones （[010], [100] and [110]） were obtained. The lattice fringes on HRTEM images along [010] have spacings of 0.319 nm. These fringes are interpreted as periodic alterations of two tetrahedral （T） sheets and one octahedral （O） sheet （-TT-O-TT-O-）. We have directly observed trioctahedral and dioctahedral individual palygorskite particles along [100]. They are all presented as dark lines along [001], but the width of dark lines corresponding to trioctahedral crystals （0.913 nm） is twice that of the dioctahedral ones （0.456 nm）. This is because the trans.sites are occupied by cations in trioctahedral palygorskite. The width of dark lines along [110] is 1.024 nm, a bit thinner than the theoretical spacing （1.044 nm）. This is because water molecules quickly leave the structure upon the irradiation by the electron beam.     

含金毒砂中晶格金的确定及其形成机理研究

利用电子探针(EPMA)和高分辨透射电子图像(HRTEM)分析技术,对湖南黄金洞金矿含金毒砂进行了背散射电子图像、X-射线面扫描、定量微区分析、线分析以及高分辨晶体结构观测等综合研究。结果表明,含金毒砂中没有发现纳米级乃至更小粒级的超显微包体金,毒砂晶格完整,无任何“异构体”,Au散布于整个毒砂颗粒中,以晶格金形式存在。此外,金含量在不同的生长环带中有显著变化,表明Au是在毒砂形成过程中进入其晶格的。金的加入导致毒砂晶体结构中(100)面网间距局部变宽,晶胞参数也发生了微弱变化,a轴变长。详细分析认为,Au主要是以Au~(3+)替代Fe~(3+)进入AsS~(3-)八面体空位中的,Eh值变化可能是控制毒砂中晶格金形成的主要因素。     

美国内华达卡林金矿之含金FeS2微晶中不可见金的TEM研究和地球化学模型

透射电子显微术的研究表明,美国内华达州卡林金矿中环绕黄铁矿大 晶体的Fe的硫 化物微晶乃是白铁矿。该白铁矿含Au和As,并在其中有纳米尺度的似带状区。相对于邻区 而言,似带状区相对富As。因而提出：似带状区还相对富晶格金。根据所得出的方解石中三 价阳离子的分配系数方程认为,Au3＋阳离子是在白铁矿的非平衡(快速)结晶 作用期间,从白铁矿－溶液界面上被结合到细粒白铁矿中去的。Au3＋在白铁矿中的 配分是由非平衡分布系数(Kd')所控制的。然而,由于Au 3＋的平衡分 配系数(Kd)小,故通过平衡(缓慢)结晶作用形成的黄铁矿并不将Au 3 ＋结合到晶体中去。早期形成的细粒晶体的再结晶作用则将把REE和Au从晶体中迁移走。 相对于正常的白铁矿结构而言,较大的Au3＋和Au＋阳离子结合进入到白铁矿晶格 中,可引起局部的结构畸变,从而表现为似带状的特征。     

物理法改色前后优质淡水珍珠的超微结构特征研究

利用原子力显微镜（AFM）、场发射高分辨率扫描电子显微镜（FESEM）和场发射高分辨率透射电子显微镜（HRTEM）对物理法改色前后的优质淡水珍珠表面进行了细致的观察。通过对比分析珍珠在微米级至纳米级的范围内微结构及超微结构特征的变化,证明珍珠质层是天然的纳米材料;改色前后珍珠的红外光谱分析及XRD分析对物理法改色珍珠机理是由于微量MnCO3在γ射线辐照下氧化成Mn2O3或MnO2所致的说法给予否定;由红外光谱测试结果可知物理法改色珍珠呈色机理与珍珠中有机物的辐照化学变化有关,并且物理法改色珍珠伴色的呈色机理与珍珠的文石纳米粒径效应亦无明显的相关性。     

High resolution transmission electron microscopy evaluation of silica glaze reveals new textures

We present the first nanoscale investigation of silica glaze. High resolution transmission electron microscopy of a rock coating from the Ashikule Basin, Tibetan Plateau, reveals the presence of spheroids composed predominantly of silicon and oxygen with diameters ranging from 20 nm to 70 nm. While silica glaze spheroids co‐exist with manganese‐rich rock varnish in the same sample, the different rock coatings are texturally and physically distinct at the nanoscale. These observations are consistent with a model of silica glaze formation starting with soluble aluminum‐silicon (Al‐Si) complexes [Al(OSi(OH)³)²⁺], mobilized with gentle wetting events such as dew or frost. The transition between complete and partial wetting on silica surfaces rests at about 20–70 nm for liquid droplets. Upon crossing this transition, a metastable wetting film would be ruptured, initiating formation of silica glaze through spheroid deposition. Copyright © 2010 John Wiley & Sons, Ltd.     

广西合浦优质白色海水珍珠表面超微结构特征研究

利用场发射高分辨率扫描电子显微镜（FESEM）、原子力显微镜（AFM）和场发射高分辨率透射电子显微镜（HRTEM）对广西合浦所产的具伴色和不具伴色的优质白色海水珍珠表面进行了系统的观察。通过对比分析珍珠在微米级至纳米级范围内微结构及超微结构特征的变化,证明了珍珠质层是天然的纳米材料,组成文石晶层的3μm文石小晶片是由10～60 nm的纳米文石小晶粒组成,珍珠伴色与其表面生长机理纹规则与否相关。     

阳山金矿带金的赋存状态及其对成矿过程的指示意义

阳山金矿带是西秦岭金矿带已探明金储量最大的独立金矿区,其矿化样式主要为微细浸染状矿化,其次为石英脉型矿化,可见金与“不可见金”均有发育,该金矿带是研究造山型金矿金赋存状态的理想地区,其研究成果对理解金成矿作用和过程以及指导选矿工艺具有重要意义。论文在翔实的野外地质调查和显微观察基础上,将成矿期划分为早阶段(黄铁矿石英)、主阶段(黄铁矿毒砂绢云母石英)和晚阶段(辉锑矿石英方解石),综合应用电子探针、激光剥蚀电感耦合等离子体质谱、电感耦合等离子质谱仪、高分辨率透射电镜、X射线粉晶衍射等技术,剖析阳山金矿带不同成矿阶段金的赋存状态,进而探讨其对成矿过程的指示意义。研究表明：成矿早、主阶段以微细浸染状硫化物矿化为主,金主要以晶格金的形式赋存于黄铁矿和毒砂中;而成矿晚阶段以脉状矿化为主,金主要以自然金的形式存在。金的赋存状态的变化,指示从成矿早阶段到晚阶段,成矿温度、压力逐渐降低,成矿流体成分由富As流体演化为相对贫As且富Sb的流体。