一种潜在的地质压力计：流体包裹体子矿物的激光拉曼光谱测压法

高温高压下矿物的拉曼原位测量表明，某些拉曼活性的物质其拉曼位移与压力之间具有良好的线性关系。这一特性使我们能够通过测量矿物包裹体中含有这些子矿物的拉曼位移以确定矿物的形成压力。与目前常采用的共存矿物对压力计以及流体包裹体的CO2等容线法等压力测定方法相比，该方法具有快速、方便和准确的特点。由于包裹体中可以存在各种不同的子矿物以及不同的溶液物质，因此系统研究包裹体中一切可能存在的矿物或物质的拉曼位移与温度和压力之间的关系将可以提供一种方便、准确的地质压力测量手段。     

Spectroscopic evidence for pressure-induced phase transitions in diopside

 Raman spectra of diopside were collected from atmospheric pressure to 71 GPa. The pressure dependences of 22 modes were determined. Changes occurred in the spectra at three different pressures. First, at approximately 10 GPa, the two Raman modes at 356 and 875 cm⁻¹ disappeared, while the mode at 324 cm⁻¹ split into two modes, diverging at this pressure with significantly different pressure shifts; second, at approximately 15 GPa, a small (1 to 2 cm⁻¹) drop in several of the frequencies was observed accompanied by changes in the pressure dependency of some of the modes; and third, above 55 GPa, the modes characteristic of chains of tetrahedrally coordinated silicon disappeared, while those for octahedrally coordinated silicon appeared. The first change at 10 GPa appears to be a C2/c to C2/c transition involving a change in the Ca coordination. The third change above 55 GPa appears to be a change in the silicon coordination. At 15 GPa, it is suggested that a change in compressional mechanism takes place. Received: 14 November 2000 / Accepted: 9 January 2002     

Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

碱性玄武岩中的某些巨晶单斜辉石──Ⅱ:穆斯堡尔谱──兼论单斜辉石的异常穆斯堡尔谱和铁结构态的测定

本文对辽宁宽甸碱性玄武岩中巨晶单斜辉石进行穆斯堡尔谱研究。应用晶体结构研究结果较合理地解释了单斜辉石的异常穆斯堡尔谱。结合XRD讨论了单斜辉石中Fe结构态的测定以及穆斯堡尔谱的可应用性。巨晶应结晶于相当氧化的环境。     

利用漫反射光谱鉴定红粘土中针铁矿和赤铁矿

针铁矿(Gt)和赤铁矿(Hm)是广泛存在于土壤和沉积物中的重要铁矿物。这两种矿物在土壤和沉积物中含量很低,常规的测试手段很难有效地测定其含量。利用反射光谱联合加热处理的方法,可对土壤及沉积物样品中针铁矿和赤铁矿进行定性或半定量测定。实验结果显示,样品加热到300℃后,针铁矿的反射光谱的一阶导数特征峰发生了变化,赤铁矿的一阶导数特征峰却没有明显的变化。因此加热前后样品反射光谱一阶导数的变化取决于针铁矿和赤铁矿的含量。利用这种方法估计黄土高原第三纪红粘土样品中的赤铁矿含量约为0.3%～0.4%,针铁矿含量约为0.5%～1%。     

Intercalation of kaolinite with acetamide

Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH₂ groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm^–1. Secondly, the appearance of additional bands at ∼3600 cm^–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm^–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH₂ deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm^–1 become a single band at 1680 cm^–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm^–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group. Received: 4 February 1998/ Revised, accepted: 30 June 1998     

Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li 2Mg 3Fe 3+ 2Si 8O 22(OH) 2

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.     

Confocal laser scanning microscopy and Raman imagery of ancient microscopic fossils

Among all problems confronting the study of ancient permineralized (petrified) microscopic fossils, two stand out, the need for (1) accurate documentation of their three-dimensional morphology, and (2) direct analysis of their chemical composition and that of their surrounding mineral matrices. To address these problems we demonstrate the use of two techniques that we have recently introduced to Precambrian paleobiology: confocal laser scanning microscopy and Raman imagery. These techniques, both of which are non-intrusive and non-destructive, can provide data by which to characterize, in situ and at micron-scale resolution, the cellular and organismal morphology of thin section-embedded organic-walled fossils. In addition, Raman imagery provides direct analyses of the molecular–structural composition of the kerogenous components of such fossils and of their surrounding matrices, and a means to assess quantitatively the geochemical maturity of the preserved organics. Use of these techniques for studies of ancient microscopic fossils can provide information in three dimensions at high spatial resolution about their morphology and cellular anatomy, taphonomy and fidelity of preservation, composition and mode of preservation, and their biogenicity and syngenetic origin with the rocks in which they occur.     

The effect of thermal treatment on the 57Fe Mössbauer spectrum of beryl

Mössbauer spectra (MS) of blue, green and yellow beryl (ideally Be₃Al₂Si₆O₁₈) containing approximately 1% of iron were obtained at 295 and 500 K. Room temperature (RT) spectra of both blue and green samples showed the presence of an asymmetric Fe²⁺ doublet (ΔE _Q~2.7 mm/s, δ~1.1 mm/s), with a very broad low-velocity peak. There is no clear evidence for the presence of a ferric component. The MS of the yellow sample at RT consists of an intense central absorption with parameters typical for Fe³⁺ (ΔE _Q~0.4 mm/s, δ~0.29 mm/s), plus an apparently symmetrical Fe²⁺ doublet. This sample acquires a light-blue shade upon heating in air at about 620 K. Thermal treatments at high temperatures caused no significant changes in the MS, but the green and yellow beryl acquire a blue colour. All these results are interpreted in relation to the existence of channel water and the distribution of iron among the available crystallographic sites.     

Geology and geochemistry of Iberian roofing slates

This article analyzes the geochemical and mineralogical composition of the roofing slate deposits of the Iberian Peninsula. Most roofing slate deposits are found on Middle and Upper Ordovician terrains, although there are also deposits in the Ediacaran, Cambrian and Devonian terrains. Samples of slate were taken in most of the active quarries of the Iberian Peninsula, and being analyzed by X-ray Diffraction and Fluorescence. Each lithotect or slate productive formation has its own specific proportions of major and trace elements, being able to differentiate between them by using these relationships. This fact is particularly interesting in geological exploration and prospecting, as it allows knowing exactly the slate lithotect, and also for restoration work in the architectural heritage, due to the ability of identifying the source of the original slate tiles.