海南蓬莱蓝宝石的光致发光谱学特征及意义

从光致发光光谱角度探讨了海南蓬莱蓝宝石的呈色机理.结果发现:与蓝宝石吸收光谱的500～700 nm吸收宽带相比,在500～720 nm发光波段内存在566.8 nm锐峰、600 nm左右肩峰和Cr~(3+)的694.2 nm特征峰.600 nm肩峰与其吸收峰镜像对称,566.8 nm处锐峰的产生原因复杂.600 nm肩峰可能与Fe~(2+)-Fe~(2+)离子对的电子跃迁有关;566.8 nm锐峰因532 nm激光激发Fe~(2+)-Ti~(4+)或Fe~(2+)-Fe~(3+)间的电荷迁移带,通过晶格造成Si~(4+)、Mg~(2+)等微量杂质离子敏化而产生.光致发光谱中呈现更多谱峰,能呈现离子跃迁时不同离子间发生的相互作用,为500～700 nm吸收宽带由不同致色机制的叠加给出了直接证明,是一种能全面地研究宝石矿物中致色元素能级结构的有效方法.     

黑龙江穆棱地区宝石级锆石成因探讨

利用基本的宝石学方法、紫外可见光分光光度计、红外光谱仪、激光拉曼探针和激光剥蚀等离子质谱技术(LA-ICP-MS)分析了黑龙江穆棱玄武岩风化冲积物中宝石级锆石的宝石学性质、谱学特征、包裹体特征、微量元素组成及U-Pb年龄。宝石学性质表明锆石为优质的、可直接加工利用的宝石原料;谱学特征显示锆石为未经历后期改造的高型岩浆锆石,且含有磷灰石、锆石和赤铁矿包裹体;LA-ICP-MS分析表明锆石具有明显的Ce正异常,富集重稀土元素[(Yb/Sm)N=21～63)]和HFSE元素,Th/U均大于1(1个数据例外);ΣREE较高,含量在1765×10-6～2374×10-6,与基性锆石相似;明显的Ce异常和赤铁矿包裹体说明锆石形成于氧化环境;根据Ti-in-Zircon地质温度计计算,锆石结晶的最低温度为646～737℃;U-Pb年龄为9.39±0.4Ma代表锆石的结晶年龄。基于本实验数据和前人研究成果,认为锆石巨晶形成于富集CO2的氧化环境并且与地幔的交代作用有关,是岩石圈减薄作用发展到一定阶段(衰退期)的产物。     

山东昌乐锆石的热处理实验及呈色机理研究

对山东昌乐锆石进行了一系列不同温度、不同气氛的热处理实验,并通过紫外-分光吸收光谱对锆石的颜色及其变化进行分析,探讨了昌乐锆石的呈色机理。结果显示,锆石在氧化条件下变成无色、黄色或橙色,在还原条件下产生无色,且所有样品都在400℃时颜色发生明显改变。研究表明,锆石的红色、红褐色是由空穴色心所致,锆石的黄色是由于样品中Fe3+造成的染色;锆石无色效果的改色所需温度较低,效果较好,具有巨大的商业价值。     

西藏多龙矿集区波龙、多不杂斑岩铜金矿床岩体锆石Ce4+/Ce3+比值及氧逸度特征

波龙、多不杂斑岩铜金矿床是青藏高原中部发现的两个大型斑岩铜金矿床。对波龙、多不杂斑岩铜金矿床含矿花岗闪长斑岩和不含矿花岗闪长斑岩的锆石Ce~(4+)/Ce~(3+)比值以及氧逸度等特征进行研究,并且通过计算得到了3个含矿花岗闪长斑岩的锆石Ce~(4+)/Ce~(3+)比值分别为536.03,492.18,454.02;1个不含矿的花岗闪长斑岩的锆石Ce~(4+)/Ce~(3+)比值为0.67。说明波龙、多不杂斑岩矿床中与成矿相关的岩体具有相对更高的氧化状态。对比西藏冈底斯成矿带中的斑岩矿床、云南中甸岛弧成矿带中的烂泥塘斑岩铜矿床、金沙江-红河成矿带中的马厂箐、铜厂铜钼矿以及玉龙成矿带铜钼矿床岩体的锆石Ce~(4+)/Ce~(3+)比值,发现含矿岩体锆石Ce~(4+)/Ce~(3+)比值一般250。结合波龙、多不杂矿床的锆石Ce~(4+)/Ce~(3+)的计算结果发现Ce~(4+)/Ce~(3+)基本300,因此将锆石Ce~(4+)/Ce~(3+)300作为波龙、多不杂矿床斑岩成矿的一个地球化学标志。此外,通过(Ce/Ce~*)_D锆石氧逸度计和(X_(Ce~(4+))~(melt)/X_(Ce~(3+))~(melt))锆石氧逸度计计算得到的波龙、多不杂矿床含矿花岗闪长斑岩体的氧逸度(log(f_(O_2)))分别位于MH(磁铁矿-赤铁矿)缓冲带和FMQ(铁橄榄石-磁铁矿-石英)缓冲带之上,平均值为ΔMH+3.24和ΔFMQ+1.78,前人研究发现多不杂含矿石英斑岩的氧化状态较高,平均ΔNNO+2.4,含矿斑岩体的形成具有较高的氧逸度条件,说明高氧逸度更有利于多龙矿集区斑岩型铜矿成矿。     

地开石-高岭石混层矿物的电子顺磁共振(EPR)研究

本文首次利用EPR研究了我国北方石炭-二叠纪煤系地层粘土岩中的粗晶(1～2mm)。与粉末状地开石、高岭石、地开石-高岭石混合样的Fe~(3+)EPR谱对比证明,这些粗晶是一种地开石-高岭石(D-K)的非规则混层矿物,其单晶的EPR表明,Fe~(3+)离子有两种位置:低对称位置,引起弱各向异性的Ⅰ线,λ～0.30;高对称位置,给出强各向异性的E线,λ～0.24。这对历来认为高岭石的Fe~(3+)谱中Ⅰ线为各向同性的看法是一个有益的修正。Ⅰ呈双线(Ⅰ_1及Ⅰ_2)是鉴定这种粗晶属于D-K混层矿物的一个特征标志。     

热处理低温钠长石的EPR和X射线衍射研究

利用电子顺磁共振(EPR)和X射线衍射方法研究了天然和热处理钠长石单晶。热处理在500—850℃水热条件下完成。在外加磁场B平行于晶体c~*轴的方向上,测量了加热前后Fe~(3+)的EPR谱和线宽△B随温度和加热时间的变化。结果显示,线宽随Al、Si无序的增大而增加。由此得出结论,在低温钠长石中,Fe~(3+)位于Al~(3+)占据的T_1(o)位置,在被研究的温度范围内,Fe~(3+)未参与四面体位置T间Al、Si交换。谱线的加宽主要是由在Fe~(3+)邻近位置上Al、Si无序的增大引起的,同时与观测到的晶胞参数变化有关。在Al、Si无序更强的晶体中,Fe~(3+)谱变得极宽。     

云南中甸岛弧烂泥塘斑岩铜矿床岩体氧逸度特征及成矿意义

烂泥塘斑岩铜矿床是义敦岛弧带南段(中甸岛弧)西斑岩成矿带新发现的中型铜矿床。针对烂泥塘斑岩铜矿床含矿石英二长斑岩和不含矿石英闪长玢岩、闪长玢岩的锆石Ce~(4+)/Ce~(3+)比值、δEu值以及氧逸度等特征进行研究,并通过计算得到2个含矿石英二长斑岩体Ce~(4+)/Ce~(3+)比值分别为294.85和283.31,δEu分别为0.72和0.77;不含矿的石英闪长玢岩和闪长玢岩Ce~(4+)/Ce~(3+)比值分别为105.63和87.07,δEu分别为0.73和0.36。表明与成矿有关的岩体具有相对较高的氧化状态。对比西藏冈底斯成矿带、云南金沙江-红河成矿带中段马厂箐铜钼矿和北段玉龙成矿带铜钼矿床岩体Ce~(4+)/Ce~(3+)比值,发现含矿岩体锆石的Ce~(4+)/Ce~(3+)比值通常都大于240,而不含矿岩体锆石的Ce~(4+)/Ce~(3+)比值都小于120(邦铺矿床除外)。并且可将锆石Ce~(4+)/Ce~(3+)260、δEu0.65参数作为烂泥塘斑岩型铜矿床成矿的地球化学标志。此外,烂泥塘矿区内含矿石英二长斑岩体的氧逸度(lg(fo_2))基本位于MH缓冲对之上,平均值分别为MH+2.1和MH+1.2,含矿斑岩体具有较高的氧逸度条件。锆石U-Pb年龄与锆石Ce~(4+)/Ce~(3+)比值以及氧逸度(lg(fo_2))存在负相关关系,表明复式岩体中晚阶段侵位的岩体更有利于成矿。     

甘肃白银厂矿田锆石红外光谱特征和地质年龄估测

应用矿物红外光谱学的方法系统研究了白银厂地区7件锆石同位素年龄样品的红外光谱。测定结果表明，3件样品的吸收峰强而窄，整体线形与标准的晶质锆石谱线相符合；其余4件样品的吸收相对较弱，峰形圆钝；谱线均有不同程度向变生锆石特征谱线的演化，以变生程度最高的LGG-6为尤。根据615cm^-1吸收峰的H／M值可将所研究样品分为晶质锆石、半变生锆石和变生锆石三类，并利用锆石红外光谱特征估测了铀钍含量和地质年龄。同时还评估了相应样品的U-Pb同位素年龄的可靠性。     

碱性长石中Fe^3＋在四面体位置间交换动力学的EPR研究

在加热条件下,利用EPR方法研究了碱性长石中不同四面体位置间的Fe~(3+)、Al~(3+)交换。低温钠长石和透长石晶体分别在水热,1 kbar,500—900℃和干加热,1050℃条件下加热。在低温钠长石中,加热后Fe~(3+)线被加宽,当温度为800℃时,除T_1(o)位置外,没有出现其余四面体位置Fe~(3+)产生的谱线。透长石在1050℃加热1300h后,T_1和T_2线的相对强度发生了变化。实验表明,在碱性长石中不同四面体间Fe~(3+)、Ak~(3+)和Fe~(3+)、Si~(4+)交换与Al~(3+)、Si~(4+)交换比较,前者速度要缓慢得多。     

新疆绿柱石宝石辐照致色机制的吸收光谱研究

本文对新疆阿尔泰天然淡蓝、浅蓝宝石级绿柱石辐照前后及退火处理伴随着颜色改变的吸收光谱等进行了分析讨论,认为天然淡蓝、浅蓝色绿柱石经~(60)Co-γ辐照变成黄绿色,其原因主要归因于遂道中Fe~(2-)向Fe~(3+)的转变和八面体中Fe~(3+)和配位体O~(2-)的电荷转移。     

Raman study of radiation-damaged zircon under hydrostatic compression

Pressure-induced changes of Raman band parameters of four natural, gem-quality zircon samples with different degrees of self-irradiation damage, and synthetic ZrSiO₄ without radiation damage, have been studied under hydrostatic compression in a diamond anvil cell up to ~10 GPa. Radiation-damaged zircon shows similar up-shifts of internal SiO₄ stretching modes at elevated pressures as non-damaged ZrSiO₄. Only minor changes of band-widths were observed in all cases. This makes it possible to estimate the degree of radiation damage from the width of the ν₃(SiO₄) band of zircon inclusions in situ, almost independent from potential “fossilized pressures” or compressive strain acting on the inclusions. An application is the non-destructive analysis of gemstones such as corundum or spinel: broadened Raman bands are a reliable indicator of self-irradiation damage in zircon inclusions, whose presence allows one to exclude artificial color enhancement by high-temperature treatment of the specimen.     

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.     

湖北英山刚玉矿物学研究

湖北英山刚玉矿床是本世纪五、六十年代发现的,由于多种原因未能对其进行研究和开发利用。本文系统地研究了英山刚玉矿物学特征,测定了各种物性和参数,观测了刚玉包裹体;并利用电子探针、粉晶Ｘ射线分析、可见光谱等现代测试手段,较详细地分析了刚玉的化学成分、晶体结构及光谱特征,并进行了热处理实验研究。指出湖北英山产出的刚玉颗粒大,晶形好,颜色较浅,可用热处理的方法改成蓝色、黄色、肉红色,但由于裂隙发育,包裹体     

Mn2+和Fe3+的致色作用:来自意大利白垩纪远洋红色灰岩的启示

本文首先详细研究了含Mn2 和Fe3 的致色矿物菱锰矿、鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收光谱及其一阶导数谱,鲕状赤铁矿、云母赤铁矿和镜铁矿的可见光吸收一阶导数谱的红光区的吸收谷的位置的变化表明随赤铁矿结晶度的降低,吸收谷由586.4nm移至577.4nm,而菱锰矿展示出了Mn2 的因电子跃迁产生的四个典型吸收及其一阶导数谱上577nm的吸收谷的强度比赤铁矿相应谷的强度低一个数量级,表明其电子跃迁的致色机理与赤铁矿的染色机理完全不同。依据赤铁矿的结晶度和鲕状赤铁矿与大洋红层中赤铁矿的沉积成因相似的原则遴选出鲕状赤铁矿为含Fe3 致色矿物,依据菱锰矿是和方解石具有相似结构且为红色的原则选取菱锰矿为含锰致色矿物,并佐以化学纯氧化镁为基体配制了一系列的含菱锰矿、鲕状赤铁矿和菱锰矿及鲕状赤铁矿的两相或三相混合物。详细研究了三类混合物的可见光吸收光谱的一阶导数谱,发现含菱锰矿和含鲕状赤铁矿在573nm附近均存在一吸收谷,鲕状赤铁矿的重量分数低至0.05%时仍可见一明显吸收谷且该吸收谷移至565nm附近,菱锰矿在低至0.50%时也可见这一吸收且在低至0.11%时仍可显示出菱锰矿的信息,其575nm的吸收峰未见偏移;混合物可见光一阶导数吸收谱上鲕状赤铁矿的575nm附近的吸收谷的强度随鲕状赤铁矿的重量分数的升高而增强,而所有的配制混合物中该吸收谷的位置低于577.4nm的事实也表明为使致色矿物和氧化镁混合均匀的研磨降低了赤铁矿的结晶度。本研究表明Mn2 的电子跃迁激发和细小、结晶差的赤铁矿的染色共同造就了意大利白垩纪远洋红色灰岩的红色。     

Purplish-red almandine garnets with alexandrite-like effect: causes of colors and color-enhancing treatments

Fine gem-quality, purplish-red garnets from the Tocantins State, Brazil, were investigated for their crystal chemistry and optical properties by several spectroscopic techniques, including electron microprobe analysis, Mössbauer, Raman spectroscopy and optical absorption. Although most garnets are purplish-red, some specimens show color zoning, with deep red color in the core and purple in the outer parts. Electron microprobe analysis showed that these garnets are principally almandine–pyrope solid solution at the rim. However, at the red core, they contain also up to 7 % of spessartine. Mössbauer spectroscopy reveals that the iron content is predominantly Fe²⁺ (>99 %) in the natural garnets. The optical absorption spectra are dominated by spin-allowed and unusual high-intense spin-forbidden transitions from eightfold coordinated Fe(II) in the near infrared and visible spectral region, respectively. For the red core, in addition, three sharp bands centered in the blue part of the visible spectral range and a broad charge transfer band in the near-UV region are observed. All garnets with purplish colors show also a remarkable color-changing effect from purple in daylight light to red in incandescent light called alexandrite-like effect. Heat treatments in the 700–900 °C temperature range in oxidizing and reducing atmospheres lead to reversible and irreversible color changes which are discussed based on the microscopic changes in the Fe ion coordination and valence states.     

First diamonds from placers in Primorie

The paper reports the results obtained by the detailed studying of carbonado (the first find in a gold placer in Primorie) and a collection of diamonds that was confiscated in 1937 from a poaching small digger and was kept safe at the Nezametnyi mine (near the village of Vostretsovo), which had developed this placer deposit. In the concentrate from the placer, carbonado is associated with green corundum, various ilmenite, zircon titanian amphiboles and pyroxenes, rutile, anatase, and fragments of subvolcanic biotite picrites. All of these minerals, native aluminum, and tin occur as inclusions in the diamonds. The carbonado from Primorie was determined to be practically identical to this mineral from Brazil, has a porous structure, is characterized by orange luminescence, contains inclusions of Y, Ce, La, Ba, and Sr phosphates, and has an isotopically light composition of its carbon (¹³C from ?25 to ?32‰). Pores of the carbonado aggregates contain clusters of diamond crystals. The collection of diamonds from an unknown source included six gem-quality transparent crystals, one rounded ballas, two cuboctahedral crystals (one of greenish and the other of silver-gray color, both with outer coats), and one black carbonado grain. The data obtained on the mineralogy of the diamonds have demonstrated that they are completely identical to this mineral from kimberlites and lamproites but bear traces of intense dissolution, fragmentation, multiple recrystallization, and graphitization at defects, which are the most widespread in the ballas. One of the crystals was determined to contain inclusions: aggregates of potassic omphacite (0.50 wt % K₂O) and corundum. Ilmenite (containing up to 8 wt % MgO), titanaugite, kaersutite (4 wt % TiO₂, 0.8 wt % K₂O), and churchite (aqueous phosphate) were obtained from the core of the ballas. The titanaugite, kaersutite, and ilmenite were proven to be compositionally analogous to these minerals from picrites occurring near the placer. The carbon isotopic composition δ¹³C of the cores of the single diamond crystals varies from ?6 to ?11‰. The margins of the grains were proved to be enriched in the light carbon isotope (δ¹³C from ?19 to ?21‰). The gem-quality transparent diamond crystals are characterized by blue luminescence, and the color of luminescence in the carbonado varies from orange red in the bulk of the aggregate to yellowish green in its core. The aforementioned transformations of diamonds were likely caused by their transportation in pipes of micaceous picrites of the Jurassic meymechite complex. The carbonado are thought to correspond to the final stage of the metastable recrystallization (in pores, within the temperature range of the rutile-anatase transition) of the original isotopically heavy diamonds under the effect of various oxidizers (H₂O, CO₂, F, and others) and in the presence of catalytically acting REE, Ti, and P. The primary diamond source (kimberlite or lamproite) can be older and more distant from the study area. The complete geological analogy between the study area in Primorie, Kalimantan Island in Indonesia, and West Australia (where no sources of the placers are known) led us to consider the territory of Primorie as promising for exploration for diamondiferous placers.     

山东济南石榴石的宝石矿物学特征及颜色环带研究

山东济南宝石级石榴石赋存于市区中基性岩体北缘,产地破坏严重,缺乏系统的宝石学资料。本文利用常规宝石学仪器、傅立叶变换红外光谱、电子探针和紫外-可见光光谱对济南石榴石进行了测试。济南石榴石的围岩是矽卡岩(较早)与伟晶岩(较晚),矽卡岩中石榴石晶体呈半自形-他形,颜色以黑色-棕红色-棕黄色为主,绿色者少,主要成分是钙铁榴石,其次为钙铝榴石;伟晶岩中石榴石晶体多为菱形十二面体,颜色以绿色、黄色为主,主要成分是钙铝榴石,其次是钙铁榴石,包裹体为针状阳起石和长石。石榴石晶体颜色环带自早到晚依次呈现黑-棕红-棕黄-黄绿-绿色。绿色环带具有异常消光,Cr含量不均匀;深绿环带Fe、Ti、Cr含量高,Y含量低,其中Cr、Fe、Ti为致色元素;黑色石榴石具有高Ti含量,并含有黑色尖晶石包裹体。济南石榴石以其中含有阳起石和尖晶石包裹体等特征区别于世界其他产地的宝石级石榴石。     

福建明溪锆石的呈色机理研究

设计了一套热处理和辐照处理方法对福建明溪锆石进行处理，使之呈浅蓝色，并采用紫外一近红外吸收分光光度计对锆石的颜色及其变化进行了分析，探讨了锆石的呈色机理。分析表明，明溪锆石的褐色是由色心引起的。漂亮的浅蓝色是由Fe^2 和Fe^3 之间的电荷转移产生的。