东昆仑格尔木东部金水口片麻状富铝花岗岩锆石微区Raman光谱研究

通过对金水口片麻状富铝花岗岩中锆石的宏观形态特征和微区Raman光谱特征的研究发现，该套片麻状花岗岩中的锆石主要有2种类型：颗粒较小的简单锆石和颗粒较大的复杂锆石。复杂锆石由3部分组成：细小的残留核、浅色部分和褐色部分。简单锆石和复杂锆石核部残留锆石均为变质成因；复杂锆石的浅色部分和褐色部分均为岩浆锆石。结合锆石Raman谱线研究结果，对金水口片麻状富铝花岗岩已有的锆石U-Pb年龄进行进一步的解释，认为390-414Ma可能代表了复杂锆石的浅色部分或褐色部分的岩浆锆石的形成时代，而1600-1800MaW能记录了复杂锆石核部变质事件的时代。     

同结线附近AbxAnxDiy系列硅酸盐熔体结构及其结晶相的光谱研究

通过高温熔融，对同结线附近一系列硅酸盐熔体进行淬冷或不同速度冷却，实验获得的样品经过显微拉曼光谱分析，对比研究了AbxAnxDiy系列熔体在不同结线附近熔体结构跨相区变化情况，以及析出晶体对相应熔体结构的继承特点，熔体结构单元相对含量，在相界线两侧有某种程度的突变，熔体结构的变化对熔体的粘度，密度影响不同，拉曼光谱检测显示，硅酸盐玻璃的结构对降温速度变化不敏感，晶体对其相应熔体结构的部分继承作用，可能意味着晶体生长单元与熔体结构单元密切相关。     

花岗岩的变形构造和定位机制

通过测定花岗岩及其围岩的应变类型、组构特点和变形历史,可以推断花岗岩的定位机制。本文简单介绍了组构测量的方法和不同定位机制的判断标志,并以若干实例强调说明区域构造应力同岩桨的自然浮力和上升趋势相结合,能够产生各种不同的定位机制。     

Observation of the oxidation of galena using Raman spectroscopy

Oxidation of galena (PbS) to oxysulfates, (PbO·PbSO₄, 3PbO·PbSO₄ and 4PbO·PbSO₄)_, has been observed using Raman spectroscopy. Peaks associated with the oxidation products have been assigned. The reaction appears to be a high temperature oxidation induced by the high laser (25 mW at 514.5 nm) power density at freshly cleaved galena surfaces. Damage to the galena surface was observed visually under the microscope. Moderate laser powers (5 mW at 514.5 nm) did not result in any damage. No Raman bands were observed or expected for freshly cleaved galena because it has the rock salt structure. Laser-induced production of these oxysulfates is dramatically different from high temperature methods previously employed. This procedure will permit easy identification of galena in complex mineral ore samples. Spontaneous air oxidation of freshly cleaved galena to oxides or polysulfides was not detected.     

应用显微激光拉曼光谱分析单个流体包裹体同位素

单个流体包裹体同位素是研究特定成岩成矿（藏）阶段古流体成因和来源最有效的方法之一,在矿床、油气、地质流体和大地构造演化动力学等多个领域具有十分重要的用途。但是,目前还没有成熟的分析单个流体包裹体同位素的方法。文中在对目前国内外流体包裹体分析技术总结分析基础上,认为激光拉曼光谱是一项可以分析单个流体包裹体同位素的最有效方法,国外在该领域已经开展了许多创新性的研究工作,并取得了一些重要进展。对激光拉曼光谱分析单个流体包裹体同位素的原理和可行性进行了分析论证,提出通过对已知比值的同位素标准物质拉曼光谱测试和研究,在确定稳定同位素分子的拉曼参数和实验条件等基础上,可以建立起单个流体包裹体稳定同位素激光拉曼测试方法,从而改变目前只能依靠分析群体包裹体同位素来示踪古流体成因和来源的局限性和不确定性。     

滇西怒江－高黎贡构造带内花岗岩的侵位过程及其对特提斯演化过程的响应

高黎贡构造带的花岗岩,其分布受怒江深断裂的控制。花岗岩体沿着怒江断裂带呈南北向分布,总体表现为一个狭长的透镜体。远离怒江断裂的西侧,花岗岩具有块状构造,中粗粒结构;靠近怒江深断裂,花岗岩具有条带状构造,糜棱结构。花岗岩属于强过铝高钾钙碱性系列,其岩浆锆石SHRIMP年龄为124~118 Ma,糜棱岩化花岗岩新生黑云母Ar-Ar年龄为18~10 Ma,与北侧波密－察隅花岗岩结晶年龄（116 Ma）、变形年龄（18~12 Ma）一致,表明高黎贡花岗岩带是喜马拉雅东构造结大转弯花岗岩带的南延部分。沿着花岗岩带向南西方向依次是小龙河花岗岩（76 Ma）到盈江花岗岩（37 Ma）,逐渐变年轻,体现一个有序的侵位过程。上述特征表明,波密－察隅－高黎贡构造带花岗岩侵位时间为124~116 Ma,代表怒江深断裂的走滑高峰主体变形发生在中新世(18~10 Ma),与喀喇昆仑断裂带走滑高峰、藏南南北向裂谷系、哀牢山－红河断裂带的走滑高峰等在时间上耦合一致,可能预示中新世时期,南北向挤压、拉萨地块的东西向伸展及后期旋转,造成的周边走滑作用具有统一的应力场,属于新特提斯封闭,印度大陆向亚洲大陆碰撞、俯冲、挤压这一共同的壳幔作用的动力学过程,怒江构造带花岗岩侵位与变形记录了这一动力学过程。     

南岭地区油山岩体和坪田岩体形成年龄及其地质意义

南岭地区的油山岩体和坪田岩体位于诸广山复式岩体东侧,以前的研究认为它们都属于燕山期花岗岩。对油山岩体和坪田岩体进行的LA-ICP-MS 锆石U-Pb 年代学研究结果表明,油山岩体的成岩年龄为（213.4±3.0） Ma,坪田岩体（西北部）的成岩年龄为（238.8±2.2） Ma,因此油山岩体应属于印支期岩体,而坪田岩体可能是一个印支-燕山早期复式岩体,而非前人所划定的燕山期岩体。此外,两个岩体内含有太古代和541 Ma~1 642 Ma 的继承锆石,暗示物源区曾存在太古代和元古代地壳,经历过多期次的岩浆作用。部分油山岩体锆石在CL图像上表现出具有暗色边部的特征,这些暗色边可能与后期热液作用影响有关,其时代为燕山期,表明油山岩体在燕山期受到了流体作用的影响,坪田岩体锆石也存在较窄的暗色边,也是受后期热液作用影响所造成。     

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。     

流体包裹体激光拉曼光谱分析原理、方法、存在的问题及未来研究方向

国内外在流体包裹体激光拉曼光谱研究方面取得了大量的成果。本文回顾了流体包裹体激光拉曼光谱分析技术的发展历史,介绍了流体包裹体激光拉曼光谱技术定性和定量分析的原理和方法,指出了该技术存在的问题及未来研究方向。流体包裹体激光拉曼光谱分析主要受到样品、荧光、同位素、光化学反应、水溶性物质信号弱、气相水及水合物、子矿物等因素的影响。由于用来进行定量分析的拉曼散射截面参数明显受到压力影响,加上峰面积计算不规范化使得目前的流体包裹体激光拉曼光谱分析结果可靠性有待于重新审视。未来流体包裹体拉曼光谱分析技术应当在完善不同标准体系和标准物质光谱数据的基础上,针对不同类型包裹体采用采取不同条件,分析结果将在准确定性的基础上从相对定量向绝对定量发展。     

Compositional characteristics and Existing Forms of Major,Trace and Rare—earth Elements in Cassiterite,Dupangling Tin Ore Field,Guangxi

Trace elements in cassiterite,including Ta,W,Fe,Mn,Ti,Zr,V,Sc,Si,Al,In,Ga,Ge,Be,Bi,Ag,Sb,As,Cu,Pb,Zn,Co and REE,have been studied by many workers (Shan Zhenhua etal.,1998;Huang Zhou Tianren et al.,1987;Wu Qingsheng et al.,1988;Hu Zening,1988,Li Zhong-qing 1988 Mingzhei et al.,1988;Wang Lihua et al.,1988;Liu Kanghuai,1990).Up to now,however,most of the previous studies are concerned with trace-element variations in cassiterites of different occurrences and colors from different types of ore deposits,Data concerning the modes of occurrence of these trace elements are rare,except for the contention that Nb-Ta,Fe^2 -Mn-Fe^3 and W-Fe^3 may substitute isomorphously for Sn as pointed out by Zhou Tianren et al.(1987) and Moller et al.(1988).In this paper we are concerned with the compositional characteristics as well as the modes of occurrence of trace elements in cassiterites from quartz veins and greisens in the Dupangling tin field,Guangxi,based on multivariate statistical analyses.Tin mineralization in the Dupangling area is found associated with the medium-to fine-grained protolithionite-albite granite(γ5^2b) and its outer contacts.Cassiterite occurs,with wolframite,both in quartz veins in the contact and in greisens within the granite.^1) Spatially,greisens become dominant over quartz veins in the contact andin greisens with the granite.^1)Spatialy,gresens become dominant over quartz veins in going from the contact to the interior of the granite and with increasing depth.The greisens are of various shapes.The vein-shaped and the sheet-shaped greisens at the top of the granie are rich in quartz and the chambered greiens always constitute rich ores and contain abundant topaz or mica.Genetically,Sn,W mineralizations associated with the protolithionite-albite granite(γ5^2b) are considered to have been formed from fluid melt derived from the ore-forming magma responsible for the granite(γ5^2b).     

新疆阿尔泰伟晶岩中绿柱石拉曼光谱特征研究——以可可托海3号脉与阿祖拜328、528号脉为例

本文对新疆可可托海3号伟晶岩脉中的绿柱石与阿祖拜328、528号伟晶岩脉中的宝石级绿柱石开展拉曼光谱对比研究,获得以下主要结论: ① 阿祖拜328、528号伟晶岩脉中宝石级绿柱石以富含Ⅰ型H₂O为特征,可可托海3号脉早期形成的结构带(Ⅰ-Ⅱ带)中绿柱石以及相对富H₂O岩浆体系中形成的绿柱石(Ⅳ带)以存在Ⅰ型H₂O为主,演化程度相对较高,岩浆体系中结晶的结构带(Ⅲ带)以及岩浆-热液过渡阶段体系形成的结构带(Ⅴ带)中绿柱石以含有Ⅱ型H₂O为特征; ② 在可可托海3号脉以及阿祖拜328号、528号脉绿柱石矿物中均发现冰晶石矿物包体,指示伟晶岩岩浆含有较高的F含量;③ 绿柱石通道水类型(Ⅰ型H₂O、Ⅱ型H₂O)及相对比例,是伟晶岩岩浆-热液演化过程及其形成条件的响应,在相对氧化的岩浆体系中主要形成绿柱石矿物,而相对还原的富H₂O岩浆体系更有利于海蓝宝石形成.     

High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

Raman spectroscopy, vibrational analysis, and heating of buergerite tourmaline

Polarized Raman spectra were collected for single crystal buergerite (NaFe₃Al₆(BO₃)₃Si₆O₁₈(O_0.92(OH)_0.08)₃F) from room temperature to near 1,375°C. Vibrational assignments to features in the room temperature spectra were determined by lattice dynamics calculations, where internal BO₃ motions dominate modes near 1,300 cm⁻¹, internal SiO₄ displacements dominate modes between 900 and 1,200 cm⁻¹, while less localized displacements within the isolated Si₆O₁₈ ring mix with motions within Na, Fe, Al, F, and BO₃ environments for fundamental modes below 780 cm⁻¹. At elevated temperatures, most buergerite Raman features broaden and shift to lower frequencies up to 900°C. Above this temperature, the lattice mode peaks evolve into broad bands, while OH stretch modes near 3,550 cm⁻¹ disappear. According to Raman spectroscopy, X-ray diffraction, differential thermal analysis, and scanning electron microscopy, buergerite undergoes a complex transition that starts near 700°C and extends over a 310°C interval, where initially, Al and Fe probably become disordered within the Y- and Z-sites, and most F and all OH are later liberated. A reversible crystal-to-amorphous transition is seen by Raman for buergerite fragments heated as high as 930°C. Buergerite becomes permanently altered when heated to temperatures greater than 930°C; after cooling to room temperature, these altered fragments are comprised of mullite and Fe-oxide crystals suspended in an amorphous borosilicate matrix.     

玻璃和熔体包裹体中水含量的拉曼光谱定量测定方面的进展评述

This paper is focused on the progress in the determination of water in glasses and melt inclusions with Raman spectroscopy. Using the presented ＂Comparator Technique＂ the water content of a sample is determined by siruple comparison with a known standard. A calibration curve is not necessary. Furthermore, with this technique the water concentration in silicate melt inclusions can be determined without exposing the inclusions for measurements. This is very important for extremely water-rich melt inclusions, which would loose H2O on exposure.     

激光拉曼光谱技术在地矿领域的应用与研究进展

激光拉曼光谱技术作为一种微区定性分析方法,在地质矿产领域中的应用主要体现在流体包裹体分析、沉积有机质研究以及矿物组分鉴定方面。在流体包裹体分析中,诸如高斯-洛仑兹去卷积分峰、频移参数法、CO₂拉曼光谱压力计等方法以传统的定性分析为基础,借助峰面积、峰半高宽等拉曼特征参数与浓度、压力、同位素的良好线性关系,可对其盐度、压力、同位素进行分析; 在沉积有机质研究中,碳质物拉曼温度计可反映岩石变质级别、有机质成熟度和热演化程度; 在矿物组分鉴定中,运用点到点、点到面方式可方便快捷地对相似矿物、微小矿物进行鉴别。结合相关文献,评述了激光拉曼光谱在以上方面的最新发展,总结了现有成果和应用中存在的问题,认为这些新方法能较好地弥补传统方法的不足,但也需注意诸如荧光干扰、不同实验条件等对实验过程的便捷性、重现性和实验结果准确性的影响; 认为未来应当加强激光拉曼光谱与其他仪器之间的联用,以提高测试效率,进一步拓展拉曼光谱技术在矿产资源利用与综合研究中的应用范围,为地质工作提供更为高效的技术手段。     

显微激光拉曼光谱锆石定年方法及其应用

锆石是岩浆岩、沉积岩和变质岩中的常见副矿物,由于其具有高Th、U含量的特点,已成为地质年代学研究的理想矿物之一。显微激光拉曼光谱锆石定年方法的原理是锆石中U、Th原子自发的α衰变而引起其自身晶格的辐射损伤,锆石晶格破坏的积累和时间呈正相关关系,并且与锆石拉曼光谱半高宽Γ具有相关性。利用锆石显微激光拉曼光谱仪测量锆石特征峰的半高宽可以计算出锆石的辐射损伤累积,进而计算得到锆石发生辐射损伤所累计的时间。锆石辐射损伤定年方法具有空间分辨率高、样品制备和测试方法简单等优势。但是此方法也受控于诸多影响因素,例如锆石自身结构的不均一性、锆石发生热退火作用的速率、锆石重结晶作用及辐射损伤饱和度等对定年结果均具有影响。显微激光拉曼光谱锆石定年方法的建立将有助于判定碎屑锆石物源区、揭示岩体热演化史以及识别继承锆石经历的后期构造热事件等研究。本文从显微激光拉曼光谱锆石定年方法的基本原理、计算过程及年龄影响因素等方面对该方法进行了介绍,并通过对松多高压变质带中变泥质岩中锆石的年代学研究,结合前人的应用实例,对该方法的应用前景进行了展望,为锆石年代学研究提供新的技术手段。     

Fundamentals and Applications of Raman Spectroscopy of Carbonaceous Material(RSCM)Thermometry

This contribution attempts to summarize the principles, sample preparation, analytical procedures, influencing factors, and geological applications of Raman Spectroscopy of Carbonaceous Material (RSCM) thermometry. Irreversible graphitization of carbonaceous material in sedimentary rocks occurs during the process of reaching peak metamorphic temperature and can be effectively quantified by Raman spectroscopy. However, in addition to temperature, other factors, such as structural and compositional heterogeneity of carbonaceous materials, structural damage caused by polishing, wavelength and energy of laser used for analyses, hematite content,etc., also have significant influence on the Raman signals of carbonaceous materials. Therefore, fresh samples should be collected for analyses to eliminate the influence of hematite. Further, standard experimental procedure should be practiced to avoid the effects of polishing and laser parameter setups. Additionally, multiple (usually more than 25) analyses per sample should be carried out for deriving statistical average and uncertainty values so as to minimize the influence of sample heterogeneity. RSCM thermometry is applicable to a temperature range between 100~700 ℃, and has been widely used in many fields of geological studies, including metamorphism and deformation of orogens, sediment burial history, fault gouge characteristics and evolution, and maturation grade of carbonaceous materials,etc.     

原位低温拉曼光谱技术在人工合成CaCl_2-H_2O和MgCl_2-H_2O体系流体包裹体分析中的应用Ⅰ:低温拉曼光谱研究

利用原位低温拉曼光谱分析技术,对在设定的实验条件下合成的CaCl2-H2O体系和MgCl2-H2O体系的流体包裹体进行分析研究,结果表明低温下CaCl2水溶液和MgCl2水溶液形成的盐水合物具有各自不同的特征拉曼光谱,通过测定特征光谱,能够简易直接的鉴定这些物质,进而确定盐水体系包裹体的成分.因此,原位低温拉曼光谱技术,能够有效地测定Ca2+和Mg2+这两种盐水体系包裹体流体中常见,但显微测温过程难以观察和判别的二价阳离子.实践表明,原位低温拉曼光谱分析技术是对传统的流体包裹体显微测温技术的一个十分有效的补充,在包裹体研究领域会得到越来越广泛的应用.     

Metamorphic evolution of lawsonite eclogites from the southern Motagua fault zone,Guatemala: insights from phase equilibria and Raman spectroscopy

Lawsonite eclogite (metabasalt and metadolerite) and associated metasedimentary rocks in a serpentinite mélange from an area just south of the Motagua fault zone (SMFZ), Guatemala, represent excellent natural records of the forearc slab–mantle interface. Pseudosection modelling of pristine lawsonite eclogite reproduces the observed predominant mineral assemblages, and garnet compositional isopleths intersect within the phase fields, yielding a prograde P–T path that evolves from 20 kbar, 470 °C (M1) to 25 kbar, 520 °C (M2). The dominant penetrative foliation within the eclogite blocks is defined by minerals developed during the prograde evolution, and the associated deformation, therefore, took place during subduction. Thermometry using Raman spectra of carbonaceous material in metasedimentary rocks associated with the SMFZ eclogites gives estimates of peak‐T of ～520 °C. Barometry using Raman spectroscopy shows unfractured quartz inclusions in garnet rims retain overpressures of up to ～10 kbar, implying these inclusions were trapped at conditions just below the quartz/coesite transition, in agreement with the results of phase equilibrium analysis. Additional growth of Ca‐rich garnet indicates initial isothermal decompression to 20 kbar (M3) followed by hydration and substantial cooling to the lawsonite–blueschist facies (M4). Further decompression of the hydrated eclogite blocks to the pumpellyite–actinolite facies (3–5 kbar, 230–250 °C) is associated with dehydration and veining (M5). The presence of eclogite as m‐ to 10 m‐sized blocks in a serpentinite matrix, lack of widespread deformation developed during exhumation and derived prograde P–T path associated with substantial dehydration of metabasites within the antigorite stability field suggest that the SMFZ eclogites represent the uppermost part of the forearc slab crust sampled by an ascending serpentinite diapir in an active, moderate‐T subduction zone.     

CH4-H2O体系流体包裹体均一过程激光拉曼光谱定量分析

对南黄海盆地二叠纪地层中某石英脉中的CH4-H2O体系流体包裹体均一过程进行了激光拉曼光谱定量分析。利用甲烷与水的拉曼峰面积比值计算不同温度下流体包裹体中水溶液相中甲烷的浓度,除了在100℃附近出现最小值,随温度增加甲烷浓度呈指数增大。包裹体在214℃完全均一,均一时甲烷的浓度为0·1347mol/L。同时利用甲烷的拉曼特征对流体包裹体均一过程的内压变化作了分析。压力变化可以分为三个区间:19~100℃,随温度升高压力增大;100~150℃压力随温度升高减小;150℃之后压力迅速增大。均一温度下的内压为21·92MPa。流体包裹体内压的变化主要是由甲烷溶解行为和封闭体系的热力学特征决定的。实验表明激光拉曼光技术可以作为定量分析含甲烷流体包裹体的一种有效方法。