激光拉曼光谱法在单个流体包裹体研究中的应用进展

激光拉曼光谱法以其非破坏性、高灵敏度和高分辨率等特性,一直以来都是研究流体包裹体的重要方法之一。近年来,围绕激光拉曼光谱在流体包裹体中的应用而展开的研究主要集中在半定量-定量测试方面,即在准确定性的基础上,采用高斯-洛仑兹去卷积分峰、低温原位等定量方法获取流体包裹体的成分和含量,从而克服了激光拉曼光谱法应用于溶液中阳离子的定量分析的灵敏度、准确度较低的问题,不仅能获得流体包裹体中一些常温下不具拉曼活性的盐类物质拉曼特征峰信息,还能根据特征峰与浓度、内压之间的线性关系,进一步对盐度和压力等性质进行测定,从而拓展了激光拉曼光谱法在流体包裹体中的应用范围。本文对激光拉曼光谱法应用于分析流体包裹体成分、盐度、同位素和压力所取得的最新进展进行了评述,并认为随着分析测试技术的不断进步,激光拉曼光谱法未来的分析方向也将继续围绕多元复杂体系及其定量方面的研究展开。     

Ore-forming Fluid Characteristics of the Saishitang Cu-polymetallic Deposit in Qinghai Province, China

Saishitang Cu-polymetallic deposit is located in the southeast section of Late Paleozoic arcfold in the southeastern margin of Qaidam platform. Accoring to the geological process of the deposit,four mineralization episodes were identified: melt/fluid coexisting period(O),skarn period(A),first sulfide period(B) and second sulfide period(C),and 10 stages were finally subdivided. Three types of inclusions were classified in seven stages,namely crystal bearing inclusions(type I),aqueous inclusions(type II) and pure liquid inclusions(type III). Type I and II inclusions were observed in stage O1,having homogenization temperature from 252 to 431°C,and salinities ranging from 24.3% to 48.0%. Type I inclusion was present in stage A1,having homogenization temperature from 506 to 548°C,and salinities ranging from 39.4% to 44.6%. In stage B1,type II and III inclusions were observed,with homogenization temperature concentrating between 300–400°C,and salinities from 0.4% to 4.3%. Type II inclusions were present in stage B2,with homogenization temperature varying from 403 to 550°C. In stage C1,type I and II inclusion commonly coexisted,and constituted a boiling inclusion group,having homogenization temperatures at 187–463°C,and salinities in a range of 29.4%–46.8% and 2.2%–11.0%. Type II and III inclusions were developed in stage C2,having homogenization temperature at 124–350°C,and salinities ranging between 1.6% and 15.4%. In stage C3,type II and III inclusions were presented,with a homogenization temperature range of 164–360°C,and salinities varying from 4.0% to 11.0%. The results of micro-thermal analysis show that fluids are characterized by high temperature and high salinity in stage O1 and A1,and experienced slight decrease in temperature and dramatic decrease in salinity in stage B1 and B2. In stage C1,the salinity of fluid increased greatly and a further decrease of temperature and salinity occurred in stage C2 and C3. Fluids boiled in stage C1. With calculated pressure of 22 MPa from the trapping temperature of 284–289°C,a mineralization depth of 2.2 km was inferred. Results of Laser Raman Spectroscopy show high density of H2 O,CH4 and CO2 were found as gas composition. H-O isotope study indicates the oreforming fluids were the mixture of magmatic water and meteoric water. Physicochemical parameters of fluids show oxygen and sulfur fugacity experienced a decrease,and redox state is weakly reducing. Along with fluid evolution,oxidation has increased slightly. Comprehensive analysis shows that melt exsolution occurred during the formation of quartz diorite and that metal elements existed and migrated in the form of chlorine complex. Immiscible fluid separation and boiling widely occurred after addition of new fluids,bringing about dissociation of chlorine-complex,resulting in a great deal of copper precipitation. In conclusion,Saishitang deposit,controlled by regional tectonics,is formed by metasomatism between highly fractionated mineralization rock body and wall rock,and belongs to banded skarn Cu-polymetallic deposit.     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.     

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).     

津巴布韦金刚石中石墨包裹体及金刚石异常双折射特征分析

津巴布韦马朗(Marange)金刚石矿以产出混合习性(八面体与近立方体)金刚石为特征,其石墨包裹体仅存在于近立方体区.石墨包裹体的形态、分布及金刚石的异常双折射与应变特征,能反映其从开始结晶到被搬运至地表过程中经历的地质作用.因此,对津巴布韦混合习性金刚石及石墨包裹体的研究不仅能提供与其他产地金刚石有对比意义的数据,且...     

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.     

X-ray Raman scattering for structural investigation of silica/silicate minerals

We have performed X-ray Raman scattering (XRS) measurements on the oxygen K and silicon L absorption edges of four silica minerals: α-quartz, α-cristobalite, coesite, and stishovite. We have also calculated the partial electron densities of states (DOSs) and compared these with the XRS spectra. This study demonstrates that the short-range structure around the atom of interest strongly influences the XRS spectral features. Importantly, the oxygen K-edge XRS spectra are found to reflect the p-orbital DOS while the silicon L-edge spectra reflect the s- and d-orbital DOSs, even when a product of a momentum transfer and a mean radius of a electron orbit (1s for oxygen and 2p for silicon), Qr, is close to or larger than unity. Building on this, calculations of the partial DOSs for other silica phases are presented, including ultra-high-pressure phases, which provide a good reference for further XRS study of silica and silicate minerals. XRS measurements should be performed on not only either of oxygen or silicon but also on many kinds of constituent elements to reveal the structural change of glasses/melts of silicates under extreme conditions.     

川西甲基卡花岗伟晶岩型锂矿床中熔体、流体包裹体固相物质研究

川西甲基卡二云母花岗岩和伟晶岩内发育大量原生熔体包裹体和富晶体流体包裹体。为了查明甲基卡成矿熔体、流体性质与演化特征,运用激光拉曼光谱和扫描电镜鉴定了甲基卡花岗伟晶岩型锂矿床中二云母花岗岩及伟晶岩脉不同结构带内的原生熔体、流体包裹体的固相物质。分析结果表明,甲基卡二云母花岗岩石英内熔体包裹体的矿物组合为磷灰石+白云母、白云母+钠长石、白云母+石墨;伟晶岩绿柱石内富晶体流体包裹体的矿物组合主要为刚玉、富铝铁硅酸盐+刚玉+锂辉石、锂辉石+石英+锂绿泥石;伟晶岩锂辉石内富晶体流体包裹体的矿物组合主要为磷灰石、锡石、磁铁矿、石英+钠长石+锂绿泥石、萤石、富钙镁硅酸盐+富铁铝硅酸盐+富铁硅酸盐+石英;花岗岩浆熔体与伟晶岩浆熔体(流体)具有一定的差异,成矿熔体、流体成分总体呈现出碱质元素(Na、Si、Al)、挥发分(F、P、CO_2)含量增高及基性元素(Fe、Mg、Ca)降低的特征;包裹体中子矿物与主矿物的化学成分具有一定的差别,揭示出伟晶岩熔体(流体)存在局部岩浆分异作用,具不混溶性及非均匀性。因此认为,伟晶岩熔浆(流体)为岩浆分异与岩浆不混溶共同作用的产物,挥发分含量的增高(F、P、CO_2)使伟晶岩能够与稀有金属组成各类络合物或化合物,这对于稀有金属成矿起到了至关重要的作用。     

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     

大洋多金属结核中铁锰质矿物拉曼光谱特征初探

拉曼光谱是一种快速无损的分析手段,它既可观察样品的显微结构构造,也可分析样品的成分和结构。为了丰富多金属结核的岩石矿物学特征,文章对西太平洋某海山区的多金属结核样品进行了X射线粉末衍射分析和拉曼光谱分析。X射线分析结果显示该区域样品主要含有水羟锰矿、钡镁锰矿、斜长石、钙十字沸石和石英,显微构造主要有纹层状构造、柱状构造、树枝状构造、充填构造等。通过分析对比潮湿样品和烘干样品铁锰质矿物的拉曼特征谱峰,得出结核中水羟锰矿的特征谱峰位于490 cm~(-1)、570 cm~(-1)和626 cm~(-1)附近,钡镁锰矿的特征谱峰则位于640 cm~(-1)附近,与陆地上对应矿物的特征拉曼谱峰不同。结核中的钡镁锰矿结构不稳定,经过风干或者抛磨后部分产生相变,不同显微结构中,相变情况不同。经与RRUFF数据库比对,识别出钙十字沸石、斜长石等自形晶,多分布于结核最内层,往结核外层总体减少。矿物微晶多见铁锰质矿物微晶和钙十字沸石微晶,铁锰质矿物绕其向外生长。