透视石的原位高压单晶X射线衍射研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对透视石进行了室温下的原位高压单晶X射线衍射研究。实验的最高压力为11.7 GPa,在实验压力范围内,未观察到透视石发生相变。随着压力的升高,晶胞体积逐步被压缩,体积压缩率符合三阶Birch-Murnaghan状态方程,拟合获得体模量K0为114.6(5.3)GPa。压力低于9.3 GPa时,c轴的压缩率大于a轴;在9.3~11.7 GPa压力范围内,限制于透视石结构中的水分子在高压下会阻碍硅氧四面体六元环沿c轴方向的扭曲变形,导致c轴的抗压性增强,最终a轴与c轴的被压缩程度趋于一致。通过分析多种含水环状硅酸盐矿物的高压行为,发现高压下结构中水的存在形式对含水环状硅酸盐矿物的弹性性质有重要的影响。     

缅甸紫色翡翠的致色机理——光谱和色度学研究

采用电子探针分析、能量色散X射线荧光光谱、傅里叶变换红外光谱、紫外-可见光谱和色度学方法等多种手段,对55个缅甸紫色翡翠样品进行了全面分析。结果表明,缅甸紫色翡翠的主要化学成分为SiO₂、Al₂O₃和Na₂O,含量与标准硬玉接近。色度学测试分析显示,缅甸紫色翡翠的彩度C^*主要受色度值a^*控制,而色调角h°主要由色度值b^*控制。缅甸紫色翡翠可分为两种类型:Ⅰ型紫色翡翠主要由Mn³⁺致色,并在紫外-可见-近红外光谱570 nm显示主要吸收带;Ⅱ型紫色翡翠由于Fe²⁺-Ti⁴⁺之间的电荷转移致色,在光谱540 nm和610 nm显示吸收。两种翡翠中均存在Fe³⁺的吸收峰,样品中的全铁含量决定其色调角及明度。     

宣达地区中、下三叠统含杂卤石蒸发岩测井响应及岩性识别

钾盐主要用于农业中钾肥的生产,中国是钾盐消费和进口大国,但中国钾资源少、产量低,因此钾盐勘探对中国粮食安全有重要意义。四川盆地是中国找钾的重要区域,文章运用岩芯样品、测井等资料,通过X射线粉晶衍射、元素含量测试等实验对宣达地区中、下三叠统嘉陵江组-雷口坡组含盐系典型矿物特征及岩石测井响应特征进行分析,并基于测井解释方法原理对杂卤石进行识别。结果表明,研究区钾盐矿物包括氯化盐矿物、硫酸盐矿物、碳酸盐矿物3类,固态钾盐矿物主要为杂卤石,常与石盐、硬石膏共存,具有高电阻率、高密度、高伽马、高K的特征,主要分布于T₁j^4-2、T₁j^5-2层段。     

黑青和田玉宝石矿物学及地球化学特征研究

近年国内市场出现了一种含有黄铁矿的黑青色玉石,主要产自新疆,属于和田玉中的稀少品种。本文利用常规宝石学仪器、偏光显微镜、红外光谱、拉曼光谱、X射线粉晶衍射(XRD)、电子探针(EPMA)、激光电感耦合等离子质谱(LA-ICP-MS)以及同位素质谱仪(MC-ICP-MS)对7块黑青和田玉样品的宝石矿物学和地球化学特征进行了系统分析,结果显示,样品颜色为墨绿-黑色,折射率点测1.61,相对密度3.08~3.17,摩氏硬度6.0~6.5,主要组成矿物为透闪石,次要矿物以黄铁矿为主,同时还含有少量绿泥石、绿帘石、榍石、锆石、石墨等,具有典型的纤维交织状结构;红外与拉曼光谱特征峰显示与和田玉标准谱峰一致;样品中透闪石的主要化学成分为SiO₂、MgO、CaO和FeO,Mg/(Mg+Fe²⁺)值显示部分透闪石已过渡为阳起石;根据微量元素Cr-Ni投图判别样品为白云石大理岩型成因,稀土元素含量较少,呈左倾模式;推测成矿热液主要为岩浆水,含少量变质水;样品中黄铁矿Co/Ni>1且含少量As、Se、Cu、Zn、Pb等元素,δ³⁴S介于8.87‰~20.92‰之间,推断为岩浆热液成因且硫来源于岩浆与地层硫的混合。     

尼日利亚锌尖晶石的宝石矿物学及包裹体特征研究

采用常规宝石学测试、电子探针、单晶X射线衍射和拉曼光谱等方法,深入分析了尼日利亚锌尖晶石的常规宝石学特征、化学成分、晶体结构以及包裹体特征。尼日利亚锌尖晶石呈完好的八面体晶形,强玻璃光泽、半透明,相对密度为4.48~4.61,折射率为1.792~1.794,紫外荧光灯下呈惰性。通过电子探针测试,计算其化学式为Zn_(0.87~0.92)Fe_(0.06~0.07)Al_(1.98~2.01)O₄。单晶X射线衍射揭示其为立方晶系、空间群Fd3m,晶胞参数a=8.089(2)Å,四面体键长T—O=1.953(4)Å,八面体键长M—O=1.912 9(19)Å。锌尖晶石的特征拉曼吸收峰位于418 cm^-1和659 cm^-1,分别对应E_g模式、高频T_2g(3)模式。包裹体研究显示锌尖晶石含有多种矿物包体,包括闪锌矿、钠长石、白云母、石英、绿柱石、锆石和硅铍石,结合前人研究认为尼日利亚锌尖晶石形成于富Li、Cs、Rb、Be和Ta等元素的花岗伟晶岩中。     

缅甸抹谷紫方钠石光致变色效应脱色效率研究

光致变色效应是紫方钠石最显著且极具价值的光学特征。本文通过EDXRF、FTIR、UV-VIS-NIR、D65标准光源、照度计以及色度学方法,对缅甸抹谷紫方钠石光致变色效应脱色效率进行了定量研究。紫方钠石的主量元素为Na、Al、Si和O,此外含有少量Cl和S,微量元素可含Ca、K和Fe,UV-VIS-NIR光谱存在472、540和667 nm的3个吸收峰,其中以540 nm吸收强度最大,脱色过程中,其光谱吸收峰峰位不变,但强度随时间逐渐减小,540 nm吸收峰面积在0~80 s与时间呈线性负相关(R²=0.99);脱色过程中,当照度从5000 lx升高至30000 lx时,紫方钠石脱色效率明显升高,明度L^*升高,彩度C^*降低,色品a^*降低且色品b^*升高,色调由紫色向粉色调轻微变化,是电荷转移导致F中心被破坏的直接结果。     

秘鲁粉色蛋白石的物相组成及颜色成因

采用X射线粉晶衍射、红外光谱仪、电子探针、激光剥蚀电感耦合等离子体质谱仪以及紫外可见光分光光度计对不同深浅的秘鲁产粉色蛋白石样品进行了物相组成及颜色成因的测试和分析。结果显示,粉色蛋白石的主要矿物组成为Opal-CT、坡缕石、石英和水,且水的类型较为丰富,包含了结晶水、结构水和沸石水。结合X射线粉晶衍射、红外光谱及电子探针分析认为粉色蛋白石的颜色与坡缕石有关,且通过XRD定量分析坡缕石的含量,认为其与颜色呈正相关。综合紫外-可见光光谱、电子探针和激光剥蚀电感耦合等离子体质谱结果分析,粉色蛋白石的颜色与坡缕石结构中的有机物醌和β类胡萝卜素及Mn²⁺有关,且Mn²⁺含量越多,颜色越深,同时提出了Fe³⁺对颜色的影响,发现Fe³⁺只出现在了深色样品中。     

电子探针-电感耦合等离子体质谱法研究不同种类石榴石的稀土元素配分和矿物学特征

石榴子石是变质岩和岩浆岩中一种常见的硅酸盐矿物,其类质同象非常普遍。已有资料表明,不同成分的石榴子石的颜色颇为不同,但石榴子石的成分和颜色之间相互关系尚未进行系统研究和总结。本文应用电子探针、电感耦合等离子体质谱、X射线粉晶衍射、拉曼光谱、红外光谱和紫外可见吸收光谱等手段对常见的红色（G1）、橙色（G2）、绿色（G3）和褐红色（G4）石榴石进行了系统测试,旨在揭示石榴子石成分、结构和颜色的内在关系和变异规律,以期为不同地质体中产出的石榴子石矿物学特征的总结及地质应用提供依据。研究结果表明,G1、G4样品含有较多Fe元素（Fe³⁺：0.24%、0.24%;Fe²⁺：1.01%、0.89%）;G2样品含有较高的Mn元素（2.76%）;G3样品含有很高的Cr、V元素（3453×10^-6、1458×10^-6）。类质同象对石榴石的晶体结构产生影响,晶胞参数有较大差别,分别是a=11.530nm（G1）、11.563nm（G2）、11.849nm（G3）和11.470nm（G4）。石榴石中的微量元素和稀土元素对于示踪物源及形成过程具有很强的指示意义。石榴石中的稀土元素总量分布不均匀,LREE/HREE比值小于1,表现为重稀土元素富集,Eu/Eu^*比值小于1,为Eu负异常。所有样品的Ce异常均不明显。石榴石样品的拉曼光谱呈现出峰强和峰位的明显差异也反映了类质同象的存在：G1、G4在570nm处出现Fe³⁺电子跃迁吸收峰;G2在460nm和520nm附近出现Mn²⁺电子跃迁吸收峰;G3在690nm处出现Cr³⁺电子跃迁吸收峰。紫外可见吸收光谱特征显示,红色和褐红色样品出现在570nm处的Fe³⁺电子跃迁吸收峰,与其成分中含有大量Fe有关;橙色样品于460nm和520nm附近的特征吸收峰归属于Mn²⁺,对应其主要成分中大量的Mn;绿色样品690nm处出现强的吸收峰,由Cr³⁺跃迁产生,是微量元素Cr的存在所致。研究结果表明,石榴石的颜色与其成分和结构具有良好的对应关系。     

我国首次发现的天然硅铋石的矿物学研究

硅铋石是一种极为罕见的铋的硅酸盐矿物,本次报道的天然硅铋石产于我国内蒙古自治区东乌旗朝不楞矽卡岩型铁多金属矿床中,附生在蔷薇辉石晶洞或裂隙中的透闪石纤维上。常见四面体{111}及三角三四面体晶形,一般粒径为0.07～0.15mm,颜色多为浅黄色,透明,玻璃光泽,性脆,条痕为无色,维氏硬度VHN_（100g）=487～583kg/mm²,平均535kg/mm²,摩氏硬度5,计算密度7.11g/cm³,计算折射率N=2.15。矿物化学分子式为Bi₄Si₃O₁₂。X射线衍射强线[d（Å）（I）]为4.26（85）、3.29（100）、2.77（79）、2.11（45）和1.67（33）,结构精修晶胞参数a=10.116（2）Å,V=1035.2（7）ų,空间群为I43d,Z=4。本文还对硅铋石的成因进行了初步探讨。     

河南绿色密玉的宝石学特征和颜色成因

河南密玉是我国重要的玉石品种,属于显晶质石英岩。前人对于河南省新密市的密玉玉石矿床进行了系统的地质学研究,但其宝石学特征和颜色成因仍存在争议。文章综合了前人的研究成果,对河南密玉中的绿色系列样品进行了常规宝石学测试、红外光谱测试、紫外-可见光光谱测试、拉曼测试以及电子探针测试研究。结果表明,密玉为结晶度较好的石英岩,主要矿物成分为α-石英,次要矿物有白云母、赤铁矿、石墨、金红石、电气石等;具有花岗变晶结构和显微细粒变晶结构;紫外-可见光光谱中可见明显的Cr³⁺特征吸收峰;密玉的绿色与含铬白云母有关,而含铬白云母的绿色则是由于其所含的微量元素Cr、V、Ni等致色元素引起的,绿色越深,Cr、Ni、V含量越高;随着Fe³⁺含量增加,样品的黄色调越明显。     

Phase transition and compression behavior of gibbsite under high-pressure

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K₀ were determined to be 49 and 75 GPa, respectively with K₀ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.     

东蒙地区夕卡岩石榴石稀土元素地球化学及其成因

东蒙地区为我国北方重要的夕卡岩型锡银铜铅锌多金属成矿区，不仅矿床发育，而且成矿种类较多，典型矿床有黄岗梁Fe（Sn）、白音诺Pb-Zn-Ag等金属和浩布高Fe（Sn）－PbZnAg（Cu）矿床。研究表明，它们都是中生代岩浆岩与本区二叠系地层相互作用的产物。本文通过对黄岗梁、白音诺和浩布高3个矿床中不同阶段的石榴石夕卡岩矿物学研究，划分出早晚两期夕卡岩石榴石矿物。早期以浅色、他形细粒、均质的钙铁榴石为主，多形成环带的核心；晚期以深色、半自形中粗粒、弱非均质的钙铝榴石为主，多构成环带的边部。同时采用ICP－MS方法对3其中石榴石比较发育的黄岗梁和浩布高2个矿床中石榴石单矿物进行了稀土元素含量的测定。结果表明，矿区早期的石榴石具有岩浆成因的特征，晚期石榴石具有热液交代成因特征，即东蒙地区既有早期岩浆阶段的岩浆型夕卡岩，又有晚期热液交代型夕卡岩的多成因认识。     

Pressure-induced dehydration of dioptase: A single-crystal X-ray diffraction and Raman spectroscopy study

We present a synchrotron-based, single-crystal X-ray diffraction and Raman spectroscopy study of natural green dioptase (Cu₆Si₆O₁₈·6H₂O) up to ∼30 GPa at room temperature. The lattice parameters of dioptase exhibit continuous compression behavior up to ∼14.5 GPa, whereupon a structural transition is observed. Pressure–volume data below 14.5 GPa were fitted to a second-order Birch–Murnaghan equation of state with V₀ = 1440(2) ų and K₀ = 107(2) GPa, with K₀′ = 4(fixed). The low-pressure form of dioptase exhibits anisotropic compression with axial compressibility β_a > β_c in a ratio of 1.14:1.00. Based on the diffraction data and Raman spectroscopy, the new high-pressure phase could be regarded as a dehydrated form of dioptase in the same symmetry group. Pressure-induced dehydration of dioptase contributes broadly to our understanding of the high-pressure crystal chemistry of hydrous silicates containing molecular water groups.     

Static compression of the hydrous magnesium silicate phase D to 30 GPa at room temperature

Phase D is a dense hydrous magnesium silicate (ideal formula MgSi₂H₂O₆) which contains silicon cations exclusively in octahedral coordination. Measurements of the unit cell parameters of phase D were made to pressures of 30 GPa using a diamond anvil cell and employing synchrotron X-ray diffraction. A neon pressure medium was used. Using a third order Birch-Murnaghan equation of state the isothermal bulk modulus of phase D was determined as 166(±3) GPa with K′ equal to 4.1(±0.3). The compression of phase D is anisotropic with the c-axis twice as compressible as the a-axis. Above 20 GPa, however, the c/a ratio becomes pressure independent. Received: 29 July 1998/ Revised, accepted: 5 August 1998     

内蒙古阿拉善地区绿色戈壁玛瑙的宝石学特征与致色成因研究

内蒙古阿拉善地区经历数亿年的地质活动,产出颜色丰富且结构致密的戈壁玛瑙。通过常规宝石学测试、偏光显微镜及扫描电镜观察、X射线粉晶衍射、电子探针、红外光谱及紫外-可见光-近红外分光光度计等测试分析方法对绿色戈壁玛瑙的宝石矿物学特征及致色成因进行了深入研究。肉眼观察,阿拉善绿色玛瑙呈深绿色至褐绿色,微透明至不透明,相对密度、折射率、摩氏硬度等均符合石英质玉石的特点。偏光显微镜观察,绿鳞石富集于表层,并向内部呈放射状生长;方解石与石英均为隐晶质结构。扫描电镜观察,绿鳞石呈颗粒状分布于石英及方解石之间。X射线衍射分析结果表明,绿色戈壁玛瑙的物相组成主要为石英、方解石和绿鳞石。电子探针分析结果表明绿鳞石的主要化学组成为SiO₂、FeO、Al₂O₃、K₂O和MgO。红外光谱分析也显示存在绿鳞石对应基团的特征峰。表层绿鳞石在紫外-可见光-近红外分光光度计下显示出Fe²⁺与Fe³⁺的特征光谱,Fe²⁺与Fe³⁺之间的电荷转移是其...     

Single-crystal elastic constants of fluorite (CaF2) to 9.3 GPa

 The second-order elastic constants of CaF₂ (fluorite) have been determined by Brillouin scattering to 9.3 GPa at 300 K. Acoustic velocities have been measured in the (111) plane and inverted to simultaneously obtain the elastic constants and the orientation of the crystal. A notable feature of the present inversion is that only the density at ambient condition was used in the inversion. We obtain high-pressure densities directly from Brillouin data by conversion to isothermal conditions and iterative integration of the compression curve. The pressure derivative of the isentropic bulk modulus and of the shear modulus determined in this study are 4.78 ± 0.13 and 1.08 ± 0.07, which differ from previous low-pressure ultrasonic elasticity measurements. The pressure derivative of the isothermal bulk modulus is 4.83 ± 0.13, 8% lower than the value from static compression, and its uncertainty is lower by a factor of 3. The elastic constants of fluorite increase almost linearly with pressure over the whole investigated pressure range. However, at P ≥ 9 GPa, C ₁₁ and C ₁₂ show a subtle structure in their pressure dependence while C ₄₄ does not. The behavior of the elastic constants of fluorite in the 9–9.3 GPa pressure range is probably affected by the onset of a high-pressure structural transition to a lower symmetry phase (α-PbCl₂ type). A single-crystal Raman scattering experiment performed in parallel to the Brillouin measurements shows the appearance of new features at 8.7 GPa. The new features are continuously observed to 49.2 GPa, confirming that the orthorhombic high-pressure phase is stable along the whole investigated pressure range, in agreement with a previous X-ray diffraction study of CaF₂ to 45 GPa. The high-pressure elasticity data in combination with room-pressure values from previous studies allowed us to determine an independent room-temperature compression curve of fluorite. The new compression curve yields a maximum discrepancy of 0.05 GPa at 9.5 GPa with respect to that derived from static compression by Angel (1993). This comparison suggests that the accuracy of the fluorite pressure scale is better than 1% over the 0–9 GPa pressure range. Received: 10 July 2001 / Accepted: 7 March 2002     

Static compression of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>: linear incompressibility of lattice parameters and high-pressure transformations

The high-pressure behavior of -Fe₂O₃ has been studied under static compression up to 60 GPa, using a laser-heated diamond anvil cell. Synchrotron-based angular-dispersive X-ray diffraction shows that the sample remains in the corundum structure up to 50 GPa, but with the appearance of coexisting diffraction lines from a high-pressure phase at pressures above 45 GPa. A least-squares fit of low-pressure phase data to an Eulerian finite-strain equation of state yields linear incompressibilities of K _{a 0}=749.5 (± 18.4) GPa and K _{c 0}= 455.7 (± 21.4) GPa, differing by a factor of 1.6 along the two directions. The enhanced compressibility of the c axis may lead to breaking of vertex- or edge-sharing bonds between octahedra, inducing the high-pressure phase transformation at 50 GPa. Analysis of linear compressibilities suggests that the high-pressure phase above 50 GPa is of the Rh₂O₃ (II) structure. Continuous laser heating reveals a new structural phase transformation of -Fe₂O₃ at 22 GPa, to an orthorhombic structure with a=7.305(3) Å, b=7.850(3) Å, and c=12.877(14) Å, different from the Rh₂O₃ (II) structure.     

Structural evolution of zeolite levyne under hydrostatic and non-hydrostatic pressure: geometric modelling

This is an exploratory study on the high-pressure (HP) structural evolution of a zeolitic framework (with LEV topology) on the basis of geometric modelling and previously published accurate unit-cell constants measured by means of single-crystal X-ray diffraction. The geometric simulations for 11 P values from 0 to 5 GPa gives more insight into the HP-behaviour of levyne, showing that the anomalous elastic behaviour of this zeolite observed under hydrostatic conditions at low P (P<1 GPa) is due to a double change in the compressional mechanism. Since the geometric simulation is not restricted to using the experimentally determined cell parameters, simulations of uniaxial compression along the [001] direction and of compression in the (001) plane have been performed, shedding more light on the compression mechanisms under non-hydrostatic regimes, which are difficult to access experimentally. The mechanisms associated with compressions along different axes provide insight into the hydrostatic compression mechanisms leading to the anomalous elastic behaviour.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

X-ray diffraction studies of millerite NiS under non-ambient conditions

The high-pressure behaviour of millerite NiS up to 34.7 GPa was studied using single-crystal X-ray diffraction techniques. Under ambient pressure, 8.3, 19.2 and 26.8 GPa crystal-structure determinations were performed. No phase transition was observed and the fit of the Birch-Murnaghan equation of state gave a bulk modulus K=111(1) GPa and a pressure derivative K=5.0(1) at high pressure and room temperature. The high-temperature modification of NiS belongs to the NiAs type and has the smaller volume per formula unit. High-pressure–high-temperature X-ray diffraction studies on NiS powder indicate that the transition temperature is strongly dependent on pressure. Owing to the higher compressibility of millerite compared with that of the high-temperature phase, it is assumed that the NiAs-type is not the stable phase at high pressures.     

Compressional behavior of omphacite to 47 GPa

Omphacite is an important mineral component of eclogite. Single-crystal synchrotron X-ray diffraction data on natural (Ca, Na) (Mg, Fe, Al)Si₂O₆ omphacite have been collected at the Advanced Photon Source beamlines 13-BM-C and 13-ID-D up to 47 GPa at ambient temperature. Unit cell parameter and crystal structure refinements were carried out to constrain the isothermal equation of state and compression mechanism. The third-order Birch–Murnaghan equation of state (BM3) fit of all data gives V ₀ = 423.9(3) Å³, K _T0 = 116(2) GPa and K _T0′ = 4.3(2). These elastic parameters are consistent with the general trend of the diopside–jadeite join. The eight-coordinated polyhedra (M2 and M21) are the most compressible and contribute to majority of the unit cell compression, while the SiO₄ tetrahedra (Si1 and Si2) behave as rigid structural units and are the most incompressible. Axial compressibilities are determined by fitting linearized BM3 equation of state to pressure dependences of unit cell parameters. Throughout the investigated pressure range, the b-axis is more compressible than the c-axis. The axial compressibility of the a-axis is the largest among the three axes at 0 GPa, yet it quickly drops to the smallest at pressures above 5 GPa, which is explained by the rotation of the stiffest major compression axis toward the a-axis with the increase in pressure.