马鞍山绿松石中水的振动光谱表征及其意义

在室温和变温条件下对安徽马鞍山绿松石中水的结构特征进行红外吸收光谱和激光拉曼光谱分析研究,结果表明:绿松石中部分水分子与Cu2 结合成[Cu(H2O)4]2 水合离子,并在很大程度上制约了绿松石的颜色;马鞍山地区绿松石中结晶水的脱失温度约为303℃～310℃,结构水的脱失温度约为346℃～375℃。绿松石中H2O,OH-的振动是导致其水的激光拉曼光谱形成的主要原因,ν(OH)振动导致的强拉曼特征谱峰在3470 cm-1,3502 cm-1～3505 cm-1之间的弱谱峰则隶属3470 cm-1的次级谱峰,ν(H2O)的拉曼谱峰主峰位于3442 cm-1～3449 cm-1处。由ν(MFe,Cu-H2O)伸缩振动致平缓的拉曼谱峰主要分布在3074 cm-1～3303 cm-1附近。     

大别山区石英质玉宝石矿物学特征研究

大别山区石英质玉属新近发现的一种石英质玉（简称＂大别山玉＂）,具色彩绚丽、质地细腻温润等特点。利用偏光显微镜、扫描电子显微镜、X射线粉末衍射、化学分析、红外光谱分析等方法,重点对＂大别山玉＂的矿物组成、化学成分、物理光学性质、微结构、红外吸收光谱等特征进行研究。结果表明,＂大别山玉＂具较典型的微粒-细粒结构,主要矿物为石英,含少量的绢云母、绿泥石、萤石、黄铁矿及其它粘土矿物等次要矿物,实属石英质玉;其化学成分相对较纯,主成分为SiO2,含少量的Al2O3,CaO,MgO,Fe2O3,FeO,K2O等;其红外反射光谱以Si—O非对称伸缩振动致特征的1177,1104 cm-1谱带、Si—O—Si对称伸缩振动致800,781cm-1分裂谱带以及由Si—O弯曲振动致492 cm-1较强谱带和542 cm-1弱谱带为特征。同时,还对＂大别山玉＂的结晶度及水的赋存状态一并给予了探讨。     

CTAB-Al复合改性蒙脱石的合成及表征

采用不同CEC浓度的CTAB(十六烷基三甲基溴化铵)预先改性蒙脱石,然后再加入羟基铝离子柱撑液合成CTAB-Al-Mt复合物并利用X射线衍射分析?热重?化学分析及红外光谱分析,研究合成产物的层间结构特性,结果显示:CTAB在粘土中的加载量明显决定着CTAB-Al-Mt的层间距,铝含量。此外,在羟基铝阳离子进入粘土层间的过程中,部分层间的CTAB被置换了出来,从而引起Si(Al)—O,Si—O—Al和(M—O)Td伸缩振动波数的漂移。随着吸附水含量的减少,H—O—H弯曲振动(2ν)向高波数飘移,而O—H伸缩振动(ν1和ν3)向低波数漂移,这是由于H2O分子中的氢键较少所致。     

不同亚类硅酸盐矿物的中红外光谱学特征

利用热红外发射光谱研究了不同亚类硅酸盐矿物镁橄榄石、透闪石、蛇纹石和钠长石的红外发射光谱特征。在120oC时,通过对400～1650 cm-1的红外波段进行积分计算,发现硅酸盐矿物中镁橄榄石的发射率最高,可达到0.988,钠长石最低为0.947。硅酸盐矿物在850～1300cm-1区间均产生宽的低发射带,该发射带与硅氧四面体层中(Si,Al)-O的伸缩振动相关;在470 cm-1左右则形成相对尖锐的低发射带,与硅氧四面体层中(Si, Al)-O的弯曲振动相关。从岛状、链状、层状到架状硅酸盐矿物由于Si O2聚合程度依次增加,最强发射谷的位置依次向高频方向偏移,说明硅氧四面体中Si-O伸缩振动带的位置受到了n(Si)/n(O)比值的制约。此外,在辐射能量谱里,镁橄榄石、透闪石、蛇纹石和钠长石的最强辐射谷范围趋于变宽,依次为115、162、225和247 cm-1,反映了吸收的辐射能增加。综上可推测,硅酸盐矿物强的发射率可能与硅氧四面体中Si-O的振动模式、Si O2的聚合度、辐射能量谱中最强辐射谷的波长范围有关。     

单斜辉石中缺陷OH结合机理的变温红外光谱实验研究

利用变温红外光谱及偏振实验的结果,依据晶体化学理论及键长与振动频率的关系,从热膨胀速率这一新的角度探讨了单斜辉石中缺陷OH的结合机理。单斜辉石中OH的红外吸收峰主要有3组:3600~3620cm-1、3500~3540cm-1和3445~3465cm-1。第1组峰对应的的OH结合方式是Si4 O2- 1/2H2Al3 OH-,第3组峰对应的OH结合方式是H填充M2空位。第2组峰对应的OH结合方式复杂,可能和多个位置有关。第2和第3两组OH偶极的振动方向一致,都是M1和M2的共棱O2—O1,而第1组OH偶极的振动方向则是M2的O2—O3棱。     

鉴定热处理琥珀的关键证据

在琥珀热处理实验研究的基础上,采用常规宝石学方法和红外光谱仪,测试并跟踪收集和对比分析了实验样品热处理前、后的宝石学参数和红外光谱的变化规律及琥珀内含物的演化、改造与破坏标识,并对获得的琥珀热处理效果进行了成因分析,从而总结出鉴定琥珀热处理的关键证据。研究结果表明：（1）折射率的增加、荧光的弱化或湮灭是热处理琥珀的重要佐证;（2）盘状裂隙、红色流纹、汽化纹、龟裂纹和氧化裂纹是热处理琥珀的重要标识;（3）FTIR光谱中I=2930cm-1/I=1735cm-1比值若≤1,可视为热处理琥珀的红外光谱指纹检测依据;（4）1735,1700cm-1处的羰基（C？O）伸缩振动与1260～1156cm-1处的C—O伸缩振动吸收强度的明显增强及多峰合并的趋势反映出热处理琥珀表面的热氧化反应;C？O浓度的增加可能是热处理琥珀红色的生色团,同时又是热处理琥珀荧光的淬灭剂。     

新疆巴里坤膨润土的红外光谱分析

对巴里坤膨润土不同颜色的典型样品进行红外光谱测试分析,结果表明:巴里坤膨润土矿Ⅱ的膨润土的强吸收波谱出现在3627 cm-1(高频区)、1040 cm-1(中频区)、531 cm-1、470 cm-1(低频区)附近;5个代表样品的红外光谱曲线轮廓基本上一致,但仍存在一定的差异,不同颜色的膨润土因其化学成分的差异,在红外光谱曲线上有所不同,在3600 cm-1(高频区)附近,1#样品对红外光谱的吸收率较强,归属于Al—O—H的伸缩振动,说明1#样品蒙脱石的含量要高些;在797.64 cm-1(中频区)附近,1#、5#样品对红外光谱的吸收率要弱些,归属于Si—O—Si的反对称伸缩振动,说明SiO2的含量较低。     

人工合成图水羟砷铁矾的矿物学研究

图水羟砷铁矾是目前发现的存在于酸矿废水中的唯一的亚砷硫酸盐含铁矿物,其化学式为Fe6(AsO3)4(SO4)(OH)4.4 H2O。图水羟砷铁矾对研究酸矿废水中砷地球化学以及冶金含砷废水处理都具有重要意义。本文通过恒温水浴反应器合成该矿物,首次采用红外光谱和拉曼光谱对其表征,结果表明:位于770 cm-1处的红外特征峰来自矿物中As—O伸缩振动;位于609、663、512、455和365 cm-1处的拉曼特征峰分别来自矿物中As—OH不对称伸缩振动、As—OH伸缩振动(υ3)、AsO33-不对称弯曲振动(υ4)(512和455 cm-1)和O—As—O弯曲振动;光电子能谱结果表明矿物中As为+3价,不存在更高氧化态。低pH值和高硫酸根有利于矿物获得较好晶形;矿物在pH>3出现不谐溶解,首次测定矿物溶度积常数(Ksp)为107.7,标准吉布斯反应自由能(ΔG0f)为-3 605 kJ/mol。     

红外光谱在铁镁硅酸盐矿物类质同象研究中的应用

本文通过对柘榴石、辉石、角闪石和云母等铁镁质矿物的化学成分、光学性质和其它物性及红外吸收光谱的研究,试图找出它们的内在联系,以便用于研究矿物的类质同象变化规律。所测的矿物红外吸收光谱为中红外4000～400cm~(-1)波段的谱带特征,一般认为该波段主要是表现为硅酸盐中阴离子团的振动区。 从1、2图中可以看出所测矿物的谱带特征,铁镁硅酸盐谱带基本可分为三个波段,第一波段1100—800cm~(-1)据G.R.Hunt,J.W.Salisbury(1974),提出的硅酸盐光谱振动模式,该波段均为O—Si—O,Si—O—Si的非对称伸缩振动区。所以它们共同特点     

褐帘石的谱学特征

本文研究了6个来自不同产状、不同地区的含褐帘石样品,包括4个伟晶岩(M1663来自内蒙集宁益元兴、M7673来自内蒙集宁察汗营地区、M4960来自美国Amherst County Virginia地区、M4976来自挪威Liksviken地区)、2个矽卡岩(M1697产自河北地区、M1679产自湖南郴县地区)。通过对这6个不同产状褐帘石的电子探针主量、稀土和微量元素分析及拉曼、红外光谱学的研究来揭示褐帘石晶体化学特征。结果表明,褐帘石成分均匀,晶体内发育微裂隙,局部有脉体充填,但不同产状的褐帘石样品在主量元素如Fe O、Ca O、Al_2O_3以及REE如Ce_2O_3、Nd_2O_3、La_2O_3的含量具有明显的差别。其系统的光谱学数据表明褐帘石晶体的特征峰强度和峰位的偏移均与其组分有关,并分析指派了部分光谱峰位的归属,揭示了褐帘石中特殊谱峰位置的迁移与其元素含量、晶体结构之间的关系。拉曼光谱揭示了褐帘石单晶有20组拉曼活性谱峰(ν1～ν20),其中ν2～ν4、ν5～ν8、ν16～ν19谱峰的迁移与A位上的Ca与稀土元素之间置换作用有关;ν10～ν12谱峰是O-Si-O弯曲振动引起,其拉曼谱峰的偏移可能与Si含量有关;ν13～ν14谱峰的迁移则可能是多种元素变化共同作用的结果。褐帘石单晶红外光谱展示了13组红外活性谱峰(a-m),h-k谱峰的偏移与在M1或M3位上Fe~(3+)和Al相互替代而导致的; b-g谱峰的偏移是与硅氧四面体中Si-O非对称伸缩振动有关; OH(l-m)双峰的出现可能与M1、M3位上Fe~(3+)的含量有关。研究结果表明伟晶岩类岩石中褐帘石晶体结构中Fe~(3+)与Al~(3+)间的置换作用强于矽卡岩类岩石中的褐帘石;而矽卡岩类岩石中褐帘石晶体结构中在A位上稀土元素与Ca置换作用则大于伟晶岩类岩石中的褐帘石。     

充填红宝石的充填特征观察及命名建议

通过显微镜下观察充填红宝石内外部的充填特征、次生玻璃的形态,结合在Diamond View^TM荧光成像仪下观察红宝石基底及次生玻璃体的发光情况,对红宝石中玻璃质材料充填的"量"进行了判断.将红宝石的充填程度分为轻微充填、中度充填、明显充填3等,建议对应定名为红宝石(备注可见轻微充填现象)、红宝石(备注可见中度充填现象)、充填处理红宝石.     

Vanadium-rich ruby and sapphire within Mogok Gemfield,Myanmar: implications for gem color and genesis

Rubies and sapphires are of both scientific and commercial interest. These gemstones are corundum colored by transition elements within the alumina crystal lattice: Cr³⁺ yields red in ruby and Fe²⁺, Fe³⁺, and Ti⁴⁺ ionic interactions color sapphires. A minor ion, V³⁺ induces slate to purple colors and color change in some sapphires, but its role in coloring rubies remains enigmatic. Trace element and oxygen isotope composition provide genetic signatures for natural corundum and assist geographic typing. Here, we show that V can dominate chromophore contents in Mogok ruby suites. This raises implications for their color quality, enhancement treatments, geographic origin, exploration and exploitation and their comparison with rubies elsewhere. Precise LA-ICP-MS analysis of ruby and sapphire from Mogok placer and in situ deposits reveal that V can exceed 5,000 ppm, giving V/Cr, V/Fe and V/Ti ratios up to 26, 78, and 97 respectively. Such values significantly exceed those found elsewhere suggesting a localized geological control on V-rich ruby distribution. Our results demonstrate that detailed geochemical studies of ruby suites reveal that V is a potential ruby tracer, encourage comparisons of V/Cr-variation between ruby suites and widen the scope for geographic typing and genesis of ruby. This will allow more precise comparison of Asian and other ruby fields and assist confirmation of Mogok sources for rubies in historical and contemporary gems and jewelry.     

Tectonic environments of sapphire and ruby revealed by a global oxygen isotope compilation

Many sapphire and ruby occurrences are spatially linked with orogenic belts such as the Pan-African Orogen, the Himalayas, and regions of active or former subduction along the western margin of the Pacific Ocean. These gemstones have oxygen isotope compositions (δ¹⁸O) that span >45‰, reflecting the wide range of environments and conditions involved in corundum (Al₂O₃) formation. We compiled a global data base of sapphire and ruby δ¹⁸O, from which the following major groups of gemstones emerge: a dominant population of sapphires with δ¹⁸O centred around 5.5‰ (the mantle value) that is spatially related to regions of former subduction; a lesser population of sapphires and rubies with slightly higher δ¹⁸O that are associated with skarn and pegmatite; rubies with relatively low δ¹⁸O of 0‰–7‰ that occur in hydrothermally altered ultramafic metamorphic rocks in collision zones; and rubies with high δ¹⁸O of 14‰–25‰ that are found, almost exclusively, in Himalayan marble. The spatial distribution of the δ¹⁸O groups relative to plate boundaries provides insight into the two major periods of continental collision involved in sapphire and ruby formation: the Ediacaran collision of East and West Gondwana (the East African Orogeny) and the Cenozoic collision of India and Asia.     

Trace-element contents and cathodoluminescence of “trapiche” rubies from Mong Hsu, Myanmar (Burma): geological significance

Summary ?Mong Hsu rubies of the “trapiche” type are sporadically seen in the gem market. However, they have never been described in the field. The study of the nature of solid inclusions, the variation of trace-element contents, as well as the cathodoluminescence behaviour of six “trapiche” rubies permit the conclusion that these rubies crystallised in the same geological environment (marble-type deposit) as the normal rubies from Mong Hsu: (1) Cr and V are the main chromophorous elements in both ruby types; they act, together with Ti, as activators or quenchers for cathodoluminescence; (2) calcite, dolomite, rutile, mica, diaspore, apatite, chlorite, and feldspar are solid inclusions found in both ruby types; (3) the presence of bastn?site in trapiche ruby and fluorite in non-trapiche ruby indicates the circulation of F-bearing fluids during ruby deposition; (4) the distribution of trace-element contents in the crystal is similar for both ruby types. In the Cr₂O₃ vs. Fe₂O₃ and Cr₂O₃ vs. Fe₂O₃/TiO₂ diagrams, the population fields of Mong Hsu “trapiche” and non-“trapiche” rubies overlap. They are distinct from those of rubies and sapphires hosted in basalts from South-east Asia. Received October 30, 2001; revised version accepted March 25, 2002     

Ruby Occurrences in Turkey: Principle Characteristics

The G ksun Ophiolites in Do an ehir area (Malatya-Southern Turkey) contain corundum mineralizations with significant gem-quality (ruby). Modal mineralogical composition of ruby-bearing rocks consists of hornblende (65%-70 %), plagioclase (20%-25%), green garnet (4%-5 %), ruby (2%-3%), and opaque minerals (<1%). Although ruby shows varying colors in the groundmass, it is generally colorless and rarely very pale pink and has high relief. It has no cleavage but rotund fractures. It has highest interference colors and twinning in some poly-prismatic crystals under the microscope. Crystal sizes range from 2x10 mm up to 30x50 mm. The most remarkable properties are red to pink in color, low to medium transparency, medium to big crystal sizes, lamellar and deformation twinning, secondary liquid feathers, hollow tubes, mineral inclusions, asterism, high birefringence and refractive indices and specific gravity. Rubies show crimson red cathodoluminescence colors activated by Cr3+ in the crystal structure, which is confirmed by the Electron Probe Microanalyses (EPMA). Tectonic setting, geological environment, petrographical, mineralogical, geochemical and gemological characteristics of rubies suggest that the Do an ehir ruby mineralization can be classified into the amphibolite-hosted type of corundum deposits of Tanzania.     

Oxygen isotope systematics of gem corundum deposits in Madagascar: relevance for their geological origin

The oxygen isotopic composition of gem corundum was measured from 22 deposits and occurrences in Madagascar to provide a gemstone geological identification and characterization. Primary corundum deposits in Madagascar are hosted in magmatic (syenite and alkali basalt) and metamorphic rocks (gneiss, cordieritite, mafic and ultramafic rocks, marble, and calc-silicate rocks). In both domains the circulation of fluids, especially along shear zones for metamorphic deposits, provoked in situ transformation of the corundum host rocks with the formation of metasomatites such as phlogopite, sakenite, and corundumite. Secondary deposits (placers) are the most important economically and are contained in detrital basins and karsts. The oxygen isotopic ratios (¹⁸O/¹⁶O) of ruby and sapphire from primary deposits are a good indicator of their geological origin and reveal a wide range of δ¹⁸O (Vienna Standard Mean Ocean Water) between 1.3 and 15.6‰. Metamorphic rubies are defined by two groups of δ¹⁸O values in the range of 1.7 to 2.9‰ (cordieritite) and 3.8 to 6.1‰ (amphibolite). “Magmatic” rubies from pyroxenitic xenoliths contained in the alkali basalt of Soamiakatra have δ¹⁸O values ranging between 1.3 and 4.7‰. Sapphires are classified into two main groups with δ¹⁸O in the range of 4.7 to 9.0‰ (pyroxenite and feldspathic gneiss) and 10.7 to 15.6‰ (skarn in marble from Andranondambo). The δ¹⁸O values for gem corundum from secondary deposits have a wide spread between −0.3 and 16.5‰. The ruby and sapphire found in placers linked to alkali basalt environments in the northern and central regions of Madagascar have consistent δ¹⁸O values between 3.5 and 6.9‰. Ruby from the placers of Vatomandry and Andilamena has δ¹⁸O values of 5.9‰, and between 0.5 and 4.0‰, respectively. The placers of the Ilakaka area are characterized by a huge variety of colored sapphires and rubies, with δ¹⁸O values between −0.3 and 16.5‰, and their origin is debated. A comparison with oxygen isotope data obtained on gem corundum from Eastern Africa, India, and Sri Lanka is presented. Giant placer deposits from Sri Lanka, Madagascar, and Tanzania have a large variety of colored sapphires and rubies with a large variation in δ¹⁸O due to mingling of corundum of different origin: mafic and ultramafic rocks for ruby, desilicated pegmatites for blue sapphire, syenite for yellow, green, and blue sapphire, and skarn in marbles for blue sapphire.     

缅甸 Mong Hsu 红宝石的颜色成因

摘 要 Mong Hsu 红宝石原石具有独特的暗蓝至紫色的核心色带‚即黑心。这种黑心可以借 助热处理法加以去除‚从而改善其颜色。通过对 Mong Hsu 红宝石化学成分及可见光谱的研 究‚阐明了其颜色成因与化学成分的关系‚分析了蓝紫色调的形成机理‚这些均为红宝石的 热处理提供了理论依据。     

红外光谱-显微共焦激光拉曼光谱研究天然红宝石和蓝宝石中含水矿物包裹体特征

天然红宝石和蓝宝石的包裹体中常见典型的含水矿物包裹体,这些含水矿物包裹体容易受外界环境升温而发生改变。微量含水矿物包裹体变化会对红宝石和蓝宝石的物理和化学性质产生明显影响,该性质为宝石热处理的鉴定提供了检测思路。本文采集了天然红宝石和蓝宝石样品,用显微镜放大观察包裹体特征,结合红外光谱与显微共焦激光拉曼光谱测试研究了含水矿物包裹体的特征。结果表明:天然红宝石和蓝宝石样品中含水矿物包裹体的外观轮廓清晰,晶形完整;红外光谱在2000～3700cm~(-1)附近显示出2105～2110cm~(-1)和1977～1985cm~(-1)硬水铝石和3619cm~(-1)和3696cm~(-1)高岭石等水(H_2O或—OH等)的特征吸收峰;拉曼光谱中可见角闪石、云母、磷灰石和长石等结晶度较好的典型含水矿物包裹体的特征拉曼位移。该系列特征揭示了红宝石和蓝宝石样品中含有水的特征,可作为红宝石和蓝宝石天然成因且未经过热处理的鉴定依据。