某些幔源矿物晶体中异常消光现象的显微喇曼谱研究

异常消光是一种在幔源晶体中常可观察到的物性改变现象,然而它与晶体的真实结构之间的内在联系却至今仍未被认识清楚。本项工作试图用一种灵敏的微区结构探测新技术——显微激光喇曼谱方法研究幔源晶体中由构造作用导致的异常消光现象的结构本质。实验结果说明:上地幔高温蠕变作用对橄榄石及辉石主要感应了晶体内微区晶轴取向的变化,还未能产生明显的结构相变;不同的异常消光现象反映晶轴扭转的单位大小不同,并主要依赖于矿物晶体本身的结构特性。     

Organic geochemistry and petrology of barren and Mo–Ni–PGE mineralized marine black shales of the Lower Cambrian Niutitang Formation (South China)

Marine black shales of the Lower Cambrian Niutitang Formation in southern China host Mo–Ni–platinum group elements (PGE) mineralization confined to a phosphate- and pyrite-rich stratiform body (max. 20-cm thick). The H/C atomic ratio, carbon isotopic composition, FTIR spectra of bulk organic matter, and spectra of extractable part of organic matter indicate similar sources and thermal evolution of organic matter in barren and mineralized black shales.The morphology and relative abundance of organic particles in barren and mineralized shales are different. In barren black shales, organic particles comprise only elongated bodies and laminae 2–10 μm across or elongated larger bodies (> 10 μm) with R_max = 2.96–5.21% (Type I particles). Mineralized black shales contain Type I particles in rock matrix (90–95 vol%), small veinlets or irregular organic accumulations (Type II particles, 1–5 vol%) that display weak to well developed mosaic texture and a variable reflectance (R_max = 3.55–8.65%), and small (< 1 to 5 μm) rounded or irregular Type III organic particles (1–4 vol%) distributed within phosphate nodules and sulphide rip-up clasts. Type III particles show similar reflectance as particles of Type I in rock matrix. Type I particles are interpreted as remnants of in situ bacterially reworked organic matter of cyanobacteria/algal type, Type II as solidified products or oil-derived material (migrabitumen), and Type III particles as remnants of original organic matter in phosphatized or sulphidized algal/microbial oncolite-like bodies. Equivalent vitrinite reflectances of Type I and III particles in barren and mineralized rocks are similar and correspond to semi-anthracite and anthracite. Micro-Raman spectra of organic particles in rocks display a wide belt in the area of 1600 cm^− 1 (G belt) and approximately the same belt in the area of 1350 cm^− 1 (D belt). The ratio of integrated areas of the two belts correlate with R_max values.The Mo–Ni–PGE mineralized body is interpreted as to represent a remnant of phosphate- and sulphide-rich subaquatic hardground supplied with organic material derived from plankton and benthic communities as well as with algal/microbial oncolite-like bodies that originated in wave-agitated, shallow-water, nearshore environment.     

Structural and vibrational behaviour of fluorapatite with pressure. Part II: in situ micro-Raman spectroscopic investigation

 High-pressure Raman investigations were carried out on a synthetic fluorapatite up to about 7 GPa to analyse the behaviour of the phosphate group's internal modes and of its lattice modes. The Raman frequencies of all modes increased with pressure and a trend toward reduced splitting was observed for the PO₄-stretching modes [(ν_3a(A_g) and ν_3b(A_g); ν_3a(E_2g) and ν_3b(E_2g)] and the PO₄ out-of-plane bending modes [ν_4a(A_g) and ν_4b(A_g)]. The pressure coefficients of phosphate modes ranged from 0.0047 to 0.0052 GPa⁻¹ for ν₃, from 0.0025 to 0.0044 GPa⁻¹ for ν₄, from 0.0056 to 0.0086 GPa⁻¹ for ν₂ and 0.0046 for ν₁ GPa⁻¹, while the pressure coefficients of lattice modes ranged from 0.0106 to 0.0278 GPa⁻¹. The corresponding Grüneisen parameters varied from 0.437 to 0.474, 0.428, 0.232 to 0.409 and 0.521 to 0.800 for phosphate modes ν₃, ν₁, ν₄, ν₂, respectively, and from 0.99 to 2.59 for lattice modes. The vibrational behaviour was interpreted in view of the high-pressure structural refinement performed on the same crystal under the same experimental conditions. The reduced splitting may thus be linked to the reduced distortion of the environment around the phosphate tetrahedron rather than to the decrease of the tetrahedral distortion itself. Moreover, the amount of calcium polyhedral compression, which is about three times the compression of phosphate tetrahedra, may explain the different Grüneisen parameters. Received: 25 April 2000 / Accepted: 20 December 2000     

Characterisation of dispersed organic matter from lower Palaeozoic metasedimentary rocks by organic petrography, X-ray diffraction and micro-Raman spectroscopy analyses

Dispersed organic matter (DOM) concentrates of C-rich rocks from areas with different metamorphic characteristics were studied by organic petrography, X-ray diffraction (XRD) and micro-Raman spectroscopy analysis. The concentrates contain several types of DOM with different morphologies, reflectance, X-ray diffraction and micro-Raman characteristics.Four different morphological types were identified in the two studied areas. The different types have different distributions and their reflectance is quite variable in the four types, with a dominance of the highest reflectance values in the DOM from the area with the highest metamorphic grade.XRD analyses of samples from the areas reveal the presence of fine graphite together with non-graphitised carbons.The Raman spectral profiles show the usual bands G (1582 cm⁻¹) and D1 (1350 cm⁻¹), on the first-order Raman spectrum, and S1 (2700 cm⁻¹) on the second-order spectrum. Additional weaker bands, D2 (1620 cm⁻¹), and more rarely D3 (1500 cm⁻¹) and S2 (2900 cm⁻¹), are present. These are characteristic for disordered carbons in the different types of DOM and in both studied areas. However, the Raman parameters (D1/G intensity area ratio and the frequency and width of G band) indicate variable degrees of organisation in all DOM types.The existence of different types of DOM with different degrees of ordering in the same lithologies and metamorphic grade seems to be related to different organic precursors, as they are graphitised to different extents under the same metamorphic conditions. However, in the same lithologies and metamorphic grade, the existence of various stages of graphitisation within the same type of DOM can only be explained though the interaction of DOM with the metamorphic fluids present in the rocks. The ordering graphitisation process may be due to the existence of metamorphic fluid circulation events with a variety of compositions.     

Strain-induced amorphization of graphite in fault zones of the Hidaka metamorphic belt,Hokkaido, Japan

We report here on two distinct processes of deformation affecting graphite in fault zones of the Hidaka metamorphic belt, Hokkaido, Japan. One process involves the micrometer-scale delamination (MMD) in the stacking of graphite, and the other is the nanometer-scale delamination (NMD) in the stacking plus pulverization (P) of carbon sheets to less than 10 nm. Graphite in mylonites mainly glide along the (002) planes, and they exhibit layer separation, kink banding, and bending structures produced by MMD processes, whereas NMD + P processes induce a significant size reduction and amorphization of the graphitic structures in cataclasites, ultracataclasites, and pseudotachylytes. The strain-induced amorphization of graphite, as inferred from XRD and micro-Raman spectroscopy, corresponds well with nano-to micro-scale deformation structures observed under the HRTEM, suggesting a systematic increase of edge planes by interlayer delamination and pulverization of carbon sheets. In addition, the carbon isotopic compositions of the graphite in fault rocks have negative δ¹³C signatures, indicating a sedimentary organic origin; such graphite has a tendency to accumulate within the shear bands. Our data suggest that the graphitic structures record information on both the peak metamorphic temperatures and the deformation processes, and they show the progressive amorphization with increasing brittle deformation.     

Correlation between optical, chemical and micro-structural parameters of high-rank coals and graphite

In order to identify the parameters that best characterize the chemical and structural evolution of organic matter during coalification, the relationships between optical, chemical and micro-structural parameters in high-rank coals and natural graphite were studied. The samples include anthracites from Peñarroya–Belmez–Espiel Basin (Spain), Douro Basin (Portugal), and Alto Chicama Basin (Peru); and natural graphite from Canada, Mozambique, and Austria.Correlations between the following optical parameters were assessed: vitrinite random reflectance (R_r), Reflectance Indicating Surfaces (RIS) axis (R_MAX, R_INT and R_MIN), and RIS parameters (R_am, R_ev and R_st), as well as B_w and AI anisotropy parameters. Furthermore, the chemical parameters used were chosen according to their significant variation in coals, namely volatile matter, carbon, and hydrogen contents calculated in dry ash free basis (VM_daf, C_daf, H_daf), as well as the H/C atomic ratio. Structural organization was characterized by micro-Raman spectroscopy and XRD. Raman parameters used were the full width at half maximum (FWHM) and position of G and D1 bands on the first-order Raman spectrum, and the ID1/IG intensity area ratio. The selected XRD parameters were interlayer spacing d₀₀₂, and crystallite sizes L_a and L_c.Results show that: (i) R_MAX RIS axis seems to correlate best with chemical and micro-structural parameters; (ii) for the majority of studied samples, H_daf and H/C atomic ratio are the only chemical parameters with significant correlations with R_MAX; (iii) the FWHM of the G band of Raman spectrum shows good linear correlation with the XRD parameter d₀₀₂; and, (iv) structural organization of carbon materials, as measured by trends in their optical and crystalline parameters, is influenced by their hydrogen content (daf basis) and therefore by the H/C atomic ratio.     

Sicilian serpentinite xenoliths containing abiotic organics with nanodiamond clusters as key model for prebiotic processes

Rock fragments from the deepest parts of a buried hydrothermal system belonging to the Mesozoic Tethys Ocean entered as xenoliths in a Miocenic diatreme,hence brought to the surface,in the Hyblean Plateau(Sicily).Some xenoliths consist of strongly serpentinized ultramafic rocks bearing blebs of abiotic organic matter,where clusters of amorphous carbon nanoparticles,including nanodiamonds,are immersed.Such an occurrence conjures up established hypotheses that diamond surfaces are suitable catalytic platforms stimulating the assemblage of complex bio-organic molecules relevant to the emergence of life on Earth.The appearance of bio-organic molecules under primitive Earth conditions is one of the major unsolved questions on the origin of life.Here we report new micro-Raman spectra on blebs of abiotic organic matter from a selected xenolith.Diamond bands were related to hydrogenated nanocrystalline diamonds,with size of nearly 1-1.6 nm,formed from organics at low pressures and temperatures.In particular,diamond surfaces can give rise to crystalline interfacial water layers that may have played a fundamental role in the early biosphere evolution as a good medium for rapidly transporting positive charges in the form of hydrated protons.Nowadays,proton gradients in alkaline hydrothermal vents along oceanic ridges are generally viewed as key pre-biotic factors.In general,serpentinites span the entire geological record,including prebiotic times.These hydrous ultramafic rocks often display evidence of abiotic carbon species,both organic and inorganic,including nanodiamonds,being also capable to give rise to chemiosmotic processes and proton gradients necessary to the organisms,such as the"Last Universal Common Ancestor"(LUCA),in the prebiotic Earth.     

Characterization of fly ash from a power plant and surroundings by micro-Raman spectroscopy

Fly ash samples were collected from a Portuguese power plant that burns low-sulphur coals from South Africa, U.S.A., Colombia, and Australia. The fly ashes were collected from the hoppers of the economizers, air heaters, electrostatic precipitators, and from the stack. The power plant air monitoring system was also sampled. The fly ash characterization was conducted by micro-Raman spectroscopy (MRS). The micro-Raman spectroscopic analysis permitted an efficient identification and characterization of different inorganic and organic materials present in fly ash: quartz, hematite, magnetite, calcite, glass, aluminium and calcium oxides, and different types of organic constituents.The study of the structural evolution of the unburned carbon/char material during their path through the power plant, though the use of Raman spectra and Raman parameters reveal that despite the high temperatures they reached, these materials are still structurally disordered. However, a structural evolution occurs in the char from the economizer up to the electrostatic precipitators where the char is structurally more disordered.The different features of the Raman spectra observed for carbon particles collected from the stack, together with the high range of variation of the Raman parameters, confirm the existence of different carbon particles in the stack, i.e., char and others (probably soot).The filters from the surroundings contain a variety of carbon particles with Raman parameters different from the ones obtained in the fly ash hoppers and stack. These are diesel particles as indicated by the values of W_D1, FWHM_D1, FWHM_G, W_G and ID1/IG obtained.     

显微拉曼光谱对几种宝石矿物的无损鉴定

依据矿物的拉曼光谱前四强特征峰确定矿物的主要成分，同时特征峰的峰型、线宽，以及荧光峰可以作为宝石矿物鉴定的辅助信息。本文介绍几件宝石无损鉴定检测实践。