Effects of cation disordering in a natural MgAl2O4 spinel observed by rectangular parallelepiped ultrasonic resonance and Raman measurements

At moderate temperatures, the elastic properties of natural MgAl₂O₄ spinel differ in several significant ways from properties of synthetic spinels. Below 1000 K, the ultrasonic resonant frequencies of an ordered natural spinel change significantly after heat treatment; at higher temperatures, both types of spinels have similar resonant responses. The temperature derivatives of the elastic constants of an ordered spinel also differ from those of disordered spinels at moderate temperatures; again, at higher temperatures, both types of spinels have similar behaviors. The Raman spectra also differ below 1000 K for ordered natural and disordered spinels and are similar at higher temperatures and after cooling to ambient temperature. We associate these changes in ultrasonic resonance and Raman spectra of spinel with cation disordering at high temperature which may be quenched by cooling. We deduce estimates of the inversion parameter from the relative intensities of the two A_1g Raman modes in very good agreement with estimates made from other measurements. We find thatC ₁₁ andC ₁₂ decrease by 4 and 8%, respectively, with 20% inversion in spinel;C ₄₄ is less sensitive to cation order. These results imply that previous measurements of the adiabatic elastic constants of spinels at ambient conditions have been affected by the state of cation disorder of the specimen.     

Raman Spectroscopy of Garnet—group Minerals

The Raman spectra of the natural end members of the garnet-group minerals,which include pyrope, almandine and spessarite of Fe-Al garnet series and grossularite ,andradite and uvarovite of Ca-Fe garnet series, have been strdied.Measured Raman spectra of these minerals are reasonably and qualitatively assigned to the internal modes, translational and rotatory modes of SiO4 tetrahedra, as well as the translational motion of bivalent cations in the X site.The stretch and rotatory A1g modes for the Fe-Al garnet series show obvious Raman shifts as compared with those for the Ca-Fe garnet series ,owing to the cations residing in the Xsite connected with SiO4 tetrahedra by sharing the two edges.The Raman shifts of all members within either of the series are attributed mainly to the properties of cations in the X site for the Fe-Al garnet series andin the Y site for the Ca-Fe garnet series.     

硼酸盐矿物的振动光谱研究：Ⅰ：喇曼光谱特征

本文利用激光喇曼光谱研究了不同类型的硼酸盐矿物,讨论了它们的谱带特征及其归属。研究结果表明,具简单基团的喇曼光谱可以作出比较明确的归属,且与红外光谱结果一致,而同时具三、四配位硼的矿物,其配阴离子虽很复杂,各种谱带相互叠加,但仍可以对主要谱带作出初步的归属。     

Vibrational spectroscopy of beta-eucryptite (LiAlSiO<Subscript>4</Subscript>): optical phonons and phase transition(s)

The structural behavior of -eucryptite (LiAlSiO₄) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm^–1 (with A₂ symmetry) broadened and weakened dramatically, presumably as a result of Li⁺ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm^–1 and the linewidth of the 760 cm^–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm^–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.     

山东昌乐-临朐火山岩流体包裹体成分研究及其意义

山东昌乐-临朐地区火山岩内的橄榄石和辉石中舍有大量的流体包裹体,流体来源于地幔。采用激光拉曼光谱技术对部分火山岩流体包裹体样品进行分析,获得了包裹体中挥发分的成分和相对含量。结果表明,该区岩浆中舍有大量的CO2和水,CO2是气相包裹体中的主要成分。同时在包裹体内存在H2、CO、H2S、CH4等还原性气体,说明流体来源于还原环境。此外,少量低碳烷烃的出现为天然气无机成因提供了证据。     

Origin of natural sulphur-bearing immiscible inclusions and H2S in oolite gas reservoir, Eastern Sichuan

Based on results of microscopic observation and laser Raman analysis about fluid inclusions, multiple special forms of immiscible inclusions that contain sulphur, liquid hydrocarbon, bitumen, etc. were discovered in samples collected from the H₂S gas reservoir-containing carbonates in the Lower Triassic Feixianguan Formation in the Jinzhu-Luojia area, Kai County, Sichuan Province. Based on the lithology and burial history of the strata involved as well as measurement results of homogenization temperature of fluid inclusions, bitumen reflectivity, etc., it is concluded that the H₂S in the gas reservoir resulted from the thermal reaction between hydrocarbons in reservoir and CaSO₄ in the gypsum-bearing dolostone section at the high temperature (140°C–17°C) oil-cracked gas formation stage in Late Cretaceous. Thereafter, research on a great number of immiscible inclusions in the reservoir reveals that elemental sulphur resulted from oxidation of part of the earlier-formed H₂S and further reaction between sulphates, hydrocarbons and H₂S in geological fluids in H₂S-bearing gas reservoir at a temperature of 86°C–89°C and a pressure of 340×10⁵Pa and during the regional uplift stage as characterized by temperature decrease and pressure decrease in Tertiary. Meanwhile, gypsum, anhydrite and calcite formed at this stage would trap particles like elemental sulphur and result in a variety of special forms of immiscible inclusions, and these inclusions would contain information concerning the complexity of the fluids in the reservoir and the origin of H₂S and natural sulphur in the gas reservoir.     

二氧化碳—水体系的拉曼光谱研究

研究了使用石英管熔融封闭法分别在酸性、中性以及碱性条件下,采用ＣａＣＯ３或Ｎａ２ＣＯ３与ＨＣｌ反应制备不同浓度的ＣＯ２标准系列,并对气相、液相中的ＣＯ２进行拉曼光谱研究,得出了定量分析气相ＣＯ２所遵循的规律,即ＣＯ２的浓度与拉曼位移（１３８８．９ｃｍ－１）强度呈线性相关,为定量分析流体包裹体中ＣＯ２的含量奠定了基础。     

TROPOSPHERIC WATER VAPOR OBSERVATIONS USING A RAMAN LIDAR OVER HEFEI*

This paper presents a Raman lidar for measuring tropospheric water vapor profiles over Hefei(31.9°N,117.17°E),China.Intercomparisons of water vapor mixing ratio obtained by this Raman lidar and GZZ-59 type radiosonde observations show the good agreements when relative humidity is higher than 20%.Typical vertical profiles and seasonal variations of water vapor mixing ratio distribution are reported.Many observation eases indicate that the high moisture layer corresponds to large aerosol scattering ratios in the lower troposphere.     

Genetic Mechanism of Mineral Inclusions in Zircons from the Khondalite Series, Southeastern Inner Mongolia

The early Precambrian khondalite series is widely distributed in the Jining-Zhuozi-Fengzhen-Liangcheng area, southeastern Inner Mongolia. The khondalite series mainly consists of sillimanite garnet potash feldspar (or two-feldspar) gneiss and garnet biotite plagioclase gneiss. These gneissic rocks have commonly experienced granulite-facies metamorphism. In zircons separated from sillimanite garnet potash feldspar gneisses, many mineral inclusions, including Sil, Grt, Ky, Kfs, Qtz and Ap, have been identified by the Laser Raman spectroscopy. Generally, prograde metamorphic mineral inclusion assemblages such as Ky + Kfs + Qtz + Ap and Ky + Grt + Kfs + Qtz are preserved in the core of zircon, while peak granulite-facies metamorphic minerals including Sil + Grt + Kfs + Qtz and Sil + Grt + Kfs + Qtz + Ap are identified in the mantle and rim of the same zircon. However, in some zircons are only preserved the peak metamorphic minerals such as Sil + Grt + Kfs + Qtz and Sil + Grt + Kfs + Qtz + Ap from core to ri     

人工合成包裹体的实验研究及其在激光拉曼探针测定方面的应用

利用愈合人工水晶裂隙合成人工流体包裹体的技术，在0．5～1kb，350～800℃的范围内，对纯H2O体系、NaCl-H2O体系、KCl—H2O体系进行了人工合成包裹体实验研究。并对这些合成的包裹体进行了详细的测温学研究，证实了合成包裹体是母液成分的真实代表，完全可以用来做为自然界包裹体研究的标样。同时利用合成包裹体采集了均一、和冷冻状态下的拉曼谱，讨论了合成包裹体在激光拉曼探针测定方面的某些可能的应用。研究表明，合成包裹体是了解包裹体的形成机理和进行地质流体性质研究的一种十分有效的手段，在地质流体和实验地球化学研究领域有着广阔的应用前景。