Raman microprobe (RMP) determinations of natural and synthetic coesite

Raman microprobe (RMP) spectra of synthetic coesiste and three natural coesites from eclogite — facies rocks are provided and evaluated for characterisation purposes. The main coesite line lies at 521 cm^?1 and the other characteristic lines attributed to coesite occur at 117, 177 and 271 cm^?1. Two petrologically useful applications were (a) the confirmation of the coesite structure in very small natural crystals deduced to be coesite from petrographic observations only, and (b) the recognition of sub-microscopic crystallites of quartz in incipiently — transformed coesite in all the natural samples.     

衰减全反射-傅里叶红外光谱法快速测试干酪根样品

生油母质干酪根是石油地质工作研究的重要对象。文章利用衰减全反射(ATR)技术对干酪根样品进行傅里叶变换红外光谱分析,通过与传统压片法谱图进行峰形峰位特征、结构参数比较,表明:①ATR谱具有与压片法吸收谱类似的谱图特征;②与压片法吸收谱相比,ATR谱的吸收强度较弱;③ATR技术和压片法所获得的红外结构参数具有可比性。由于ATR技术具有无需制样、可以减少水分干扰等优点,因此可以作为干酪根样品快速测试的方法应用于干酪根样品的类型鉴别、热演化程度研究和来源对比。     

Raman spectrum of natural and synthetic stishovite

Raman spectra of natural and synthetic samples of stishovite have been measured with a micro-optical spectrometer system. These spectra have a pattern that is characteristic of rutile-structured oxides. The spectrum of synthetic stishovite is characterized by well-resolved bands at 231, 589, 753, and 967 cm^?1, which are assigned as theB _1g,E _g,A _1g, andB _2g fundamentals, respectively, of the first-order Raman spectrum of the ideal, ordered structure. Natural stishovite obtained from Meteor Crater, Arizona has a first-order Raman spectrum that is fully consistent with that of the synthetic material. The observed spectrum of the natural sample, however, is weaker and has bands in addition to those identified as fundamentals in the spectrum of the synthetic material. A broad band at ～475 cm^?1 may be indicative of glass or contaminants derived from the extraction procedure. Alternatively, this band may arise from multiphonon scattering that is enhanced by poor crystallinity or structural disorder in the natural shocked sample.     

CVD合成钻石的层状生长结构和紫外荧光特征

最近NGTC实验室检测出多批次CVD合成钻石,这些CVD合成钻石均具有明显的鉴定特征,使用钻石观测仪（DiamondViewTM）观察可见蓝色、橙红色荧光和蓝色磷光以及细密层状生长纹理,光致发光光谱中可见737 nm处的特征发光线.这些特征均与其生长结构及生长过程中进入钻石晶体中的杂质有关.笔者以最近检测过程中发现的一颗CVD合成钻石为例,使用高倍率显微技术对其层状结构的微细特征及其在钻石观测仪下的荧光特征的关系进行了详细观察和对比.结果显示,此样品与之前检测到的CVD合成钻石略有差异.此次检测到的样品在钻石观测仪（DiamondViewTM）下观察具有较宽的层状生长分区,层与层之间的分界线十分明显且在高倍显微镜下也可见到细微的生长特征.通过对样品特征的分析,了解了晶体生长过程中多阶段生长条件的变化,更直观的展现了CVD合成钻石的生长过程.     

High-pressure Raman spectroscopic study of chondrodite

Variation of Raman spectra of both natural (F-bearing) and synthetic (F-free) chondrodite samples were studied up to 400 kbar at room temperature. Ambient Raman frequencies for the synthetic sample are in general lower than those for the natural one. This is correlated with a slight expansion of the volume of the synthetic sample due to substitution of OH for F. The frequencies of all Raman bands for both samples increase monotonically with increasing pressure. The positive pressure dependences in the O−H stretch frequencies for both F-free and F-bearing samples are contrary to those for other dense hydrous magnesium silicates. A mechanism involving both the hydrogen-hydrogen repulsion and hydrogen bondings is proposed to explain the abnormal behavior. The effects of substitution of F for OH on both the ambient and high-pressure Raman spectra of chondrodite are also discussed. Received: 19 February 1998 / Revised accepted: 26 June 1998     

对部分简单形体产生的自然电位进行定量分析

本文提出了一种新的特征点法,并在前人的基础上改进了一种数值计算方法(最小二乘法),以此来确定部分具有自然电位异常简单地质体的形态(形态系数)、埋藏深度、极化角和电偶极矩。特征点法通过剖面上三个特殊点(两个极值点和零电位点)的值以及它们相互间的距离便可快速求取地质体各参数。改进的最小二乘法则是在前人的基础上加入了零电位点的计算及其它处理方法,以此来获得准确性更高的地质体各参数。两种方法都被用来计算加入±5%随机误差的理论模型数据,并在土耳其的一个实际野外数据中得到测试。结果表明所求的参数与实际参数具有较好的一致性。     

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.     

Line-broadening effects in the powder infrared spectrum of apatite

The crystallinity of natural and synthetic apatite samples is often determined from the broadening of ν ₄ PO₄ infrared absorption bands. However, various physical mechanisms contribute to the observed linewidth. In the present study, the factors determining the linewidth in the powder spectrum of synthetic fluorapatite and hydroxyapatite samples are investigated. The temperature dependence of the infrared spectrum (10–270 K) is used to assess the respective contributions of homogeneous broadening, related to the decay of phonons through anharmonic coupling, and heterogeneous broadening related to elastic strain and macroscopic electrostatic effects. This latter contribution is dominant in the investigated samples and depends on the shape of powder particles. It is discussed under the light of the theoretical modeling of the low-frequency dielectric properties of apatite based on first-principles density functional theory calculations. The linewidth of the weak ν ₁ PO₄ absorption band provides a reliable information on microscopic sources of broadening, i.e., apatite crystallinity. In comparison, the other more intense PO₄ bands are more sensitive to long-range electrostatic effects.     

俄罗斯水热法合成祖母绿的宝石学特征研究

俄罗斯水热法合成祖母绿是珠宝界较关注的产品。选用5粒俄罗斯水热法合成祖母绿样品进行了常规宝石学特征测试、电子探针成分分析、红外吸收光谱和紫外-可见吸收光谱测定。结果表明,俄罗斯水热法合成祖母绿样品以低碱、富Fe与Cr为特征,折射率和相对密度明显偏高,红外吸收光谱特征峰出现在4052cm叫附近;俄罗斯水热法合成祖母绿样品的致色元素为Cr与Fe。同时,对比分析了俄罗斯、桂林水热法合成祖母绿样品和天然祖母绿样品的宝石学特征。     

Non-Henry’s Law behavior of REE partitioning between fluorapatite and CaF2-rich melts: Controls of intrinsic vacancies and implications for natural apatites

The partitioning of rare-earth elements (REEs: Gd and multiple REEs), Sr, and Mn between fluorapatite and CaF₂-rich melts was investigated over a wide range of REE concentrations (i.e., from 0.8 ± 0.1 to 25,000 ± 2600 ppm Gd in fluorapatite) in two different sample assemblies (i.e., tightly covered Pt crucibles and sealed Pt capsules) at 1220 °C and atmospheric pressure. Attainment of equilibrium is indicated by selected reversal experiments. The partition coefficient D(Gd) decreases from ∼2 to ∼0.5 with increasing Gd in fluorapatite, hence a marked non-Henry’s Law behavior, but becomes independent of composition at and above ∼5000 and ∼1000 ppm Gd for experiments in Pt crucibles and Pt capsules, respectively. Non-Henry’s Law behavior is also observed in experiments involving multiple REEs. All REE patterns are convex upward in shape with maxima between Nd and Gd, and D(La)/D(Nd) and D(Nd)/D(Yb) decrease systematically with increasing total REEs in fluorapatite, suggesting that REE fractionations are partly related to non-Henry’s Law behavior. These experimental results and local structural data from previous electron paramagnetic resonance spectroscopic studies suggest that the non-Henry’s Law behavior of REE partitioning between fluorapatite and melt is controlled by intrinsic Ca²⁺ vacancies in the c-axis channels. The D(Sr) and D(Mn) values are independent of composition and, therefore, do not deviate from the Henry’s Law in their respective compositional ranges investigated in this study.Nonstoichiometry, such as Ca²⁺ and F⁻ vacancies in the c-axis channels, is well known in natural apatites, particularly in biogenic apatites. Therefore, the observed non-Henry’s Law behavior of REE partitioning is expected to have important implications for REE geochemical modeling involving apatites and for the uptake of REEs by natural apatites. Particularly, the non-Henry’s Law behavior of REE partitioning is at least partly responsible for the commonly observed, bell-shaped REE patterns in fossil biogenic apatites.     

Effective transfer properties of partially saturated geomaterials with interfaces using the immersed interface method

The present work aims at introducing an efficient numerical approach based on the immersed interface method to estimate the effective thermal conductivity and permeability of geomaterials as porous media with either perfect or debonded interfaces. The first part deals with the problem of the overall thermal properties of a medium containing perfectly bonded inclusions. The evolution of the homogenized properties with respect to the properties of individual constituents, the volume fraction, the spatial distribution, and the shape of inclusions is highlighted. The second part of the paper is devoted to the case of imperfectly bonded inclusions. An extension of the immersed interface method in this context makes it possible to study other aspects that have an influence on the effective properties such as the interfacial resistance and the size of inclusions. The application of the proposed numerical tool to some porous rocks in partially saturated condition shows good agreement with the available experimental results and demonstrates the performance and the flexibility of the developed procedure.Copyright © 2013 John Wiley & Sons, Ltd.     

人工合成锆石Lu-Hf同位素标样方法研究

研究了人工合成锆石并加入微量元素的实验方法和条件。人工合成锆石是以氧化锆和硅酸锂为原料,以钼酸锂和氧化钼为助熔剂,并加入其他元素如Hf、Lu、Yb、U、Th、Pb等元素,充分混匀后转入带盖铂金坩埚中,在高温马弗炉中连续加热生长形成锆石晶体。利用激光剥蚀系统与电感耦合等离子体质谱技术分析了合成锆石晶体中微量元素含量和Lu-Hf同位素组成,结果表明合成锆石晶体中Lu、Yb、U、Th、Pb等微量元素含量不均一,而Hf的含量和Lu-Hf同位素组成有很好的均一性。     

Distinction between six- and fourfold coordinated silicon in SiO2 polymorphs via electron loss near edge structure (ELNES) spectroscopy

Si K-, L- and O K-edge ELNES spectra of natural α-quartz and synthetic coesite on one side and synthetic stishovite on the other show characteristic differences that can be related, by comparison with multiple-scattering (MS) calculations, to the fourfold vs. sixfold coordination of Si in these polymorphs of SiO₂. It is shown by MS calculations on large clusters that the outer shells contribute relatively little to the overall topologies of the spectra. Therefore, distinction between fourfold- and sixfold-coordinated Si is possible even on a nm scale and probably also in amorphous substances.     

Distinguishing natural from synthetic amethyst: the presence and shape of the 3595 cm−1 peak

Summary The infrared absorption spectrum of amethyst in the region of stretching vibrations of X–OH groups reveals several bands that have been used for the separation of natural from synthetic amethyst. The intensity and shape of these bands have been measured as a function of crystallographic orientation. Using a resolution of 0.5 cm⁻¹ the 3595 cm⁻¹ band is present in all infrared spectra of natural amethyst and in some rare synthetic ones. If present in synthetic amethyst, its full width at half maximum (FWHM) is about 7 cm⁻¹ whereas it is about 3 cm⁻¹ in all natural samples. This new criterion, unlike the previous ones, seems appropriate to separate natural from synthetic amethyst in all cases.     

三种混合泥质砂岩有效介质通用电阻率模型比较

复杂泥质砂岩油气层的识别与评价一直是测井解释领域亟待解决的难点和热点问题,因此,针对复杂泥质砂岩油气层的特点,有必要研究能够描述这类储层导电规律的新导电理论。针对用于复杂泥质砂岩油气层解释的3种混合泥质砂岩有效介质电阻率模型,从理论和实验角度,进行了全面系统的比较。通过对3种有效介质通用电阻率模型建模理论基础的分析,可知混合泥质砂岩有效介质非对称模型基于HB方程和并联导电理论,对称模型基于对称导电理论和并联导电理论,而孔隙结合模型基于混合介质电导率积分方程;对称电阻率模型可用于多连续项存在的地层,而非对称电阻率模型和孔隙结合电阻率模型只允许水为连续项。对骨架不导电的纯砂岩进行模型化简,可知非对称电阻率模型和孔隙结合电阻率模型可以简化成阿尔奇公式,而对称电阻率模型能化简成类似阿尔奇公式。通过1组混合泥质砂岩人造岩样和2组分散泥质砂岩岩样以及1组骨架导电人造岩样的实验数据,验证3种有效介质通用电阻率模型均适用于混合泥质砂岩地层解释,且精度相近。     

Diffusion Coefficients of Noble Gases in Natural Minerals: An Apparent Experimental Time Dependence Caused by Domain Size Spectra

Noble gas diffusion coefficients in natural minerals are of use for evaluating geochronometric dates and other geochemical data. Usually, they are determined by degassing at elevated temperatures grain powders of natural samples containing radiogenic or cosmogenic noble gases. For conventional evaluations of diffusion parameters from degassing experiments, the grains should be uniform with respect to structure, composition, shape, and size. The shape and size prerequisites can hardly be fulfilled, because even two very narrowly meshed sieves produce spectra of domain sizes, partly because of the inhomogeneity of the minerals. Accurate determination of the actual spectrum is difficult and hardly practicable. Calculations of the fractional gas loss of a sample with a spectrum of domain sizes, presented in this study, show that almost any domain size spectrum leads to apparent diffusion coefficients that depend on the extent of degassing. The exception of this rule is given. The deviation from the physical diffusion coefficient can be several orders of magnitude as shown by examples. This effect, resulting from shape and width of the domain size spectra, possibly is responsible both for the large spread of Arrhenius parameters for the same mineral in the literature and for the deviation from linearity of some published Arrhenius lines. For limited domain size spectra and short degassing times, the formula for fractional gas loss is very similar to the formula of the fractional gas loss of a single domain size. An effective domain radius, which ensures that at least the measured diffusion coefficient for very short degassing times equals the physical diffusion coefficient, is given. In addition, the dimensionless treatment of the problem is presented that leads to a method to determine Arrhenius parameters without knowing the domain size spectrum. Accurate diffusion measurements of samples with a spectrum of domain sizes may also be possible if the domain size spectrum is taken into consideration. To this end the domain size spectra should be approximated by Taylor-expandable functions or by series of discrete domain sizes. For both cases, the formulae are given.     

基于广义S变换的裂缝分频边缘检测方法

为了在时频域刻画裂缝等边缘信息及其多尺度特征,构造了一种新的广义S变换分频边缘检测。它借鉴了小波多尺度边缘检测的思想,利用广义S变换的时频局部谱,通过不同频率尺度滤波达到突出与定位不同尺度边缘信息的目的。模型信号处理表明：广义S变换分频边缘检测方法既能准确刻画边缘奇异信息,又能反映边缘的多尺度特征,具有与小波多尺度边缘检测相似的特点。利用这一方法对实际地震资料处理的结果表明,它可以在不同频率尺度情况下有效检测断层、裂缝发育带的几何形态和空间展布。     

河南产宝石级高温高压合成钻石的谱学特征及电磁性研究

为快速鉴定高温高压(HPHT)合成钻石,前人已开展了系统的发光特征和谱学特征研究,但对比性分析较少,且对电学性质和磁学性质关注不多.本文结合常规宝石学观察、高精度谱学测试以及导电性和磁性测试,对49粒无色、黄色样品进行了深入研究和对比分析.结果表明:①铁、钴、镍等金属元素的触媒残余是HPHT合成钻石的磁性来源,测试样品...     

Mn distribution in sphalerite: an EPR study

A study on Zn replacement in sphalerite by divalent Mn has been performed by using EPR spectroscopy. Twelve natural and synthetic samples with different Mn-contents were selected for the spectroscopic investigation. The EPR spectra vary from an hyperfine sextet to a single broad line according to their Mn-content. Three components, attributed to Mn(II) in different chemical coordination (namely isolated ions, interacting ions, clusters) have been determined by means of spectral simulation. The variations of the EPR signals among the different spectra are due only to the mixing of these components, without any variation of each spectral parameter. Differing distribution of Mn(II) was, therefore, observed at a local scale. Consequently, the specific interactions driving the coalescence of Mn(II) ions to form clusters may be responsible for the banded pattern in sphalerite crystals.