Nanotopography of synthetic and natural dolomite crystals

Examination with scanning electron microscopy (SEM) and scanning force microscopy (SFM) revealed etch pits, layers and islands on dolomite crystal faces synthesized from calcite in Ca‐Mg‐Cl solutions at 200 °C and a wide variety of natural dolomites. Layers are broad, flat structures bounded by steps less than 100 nm high and greater than 1 μm wide. Islands are rounded topographic highs <20 nm high and <200 nm wide. The nanotopography of synthetic dolomite changed from islands throughout most of the reaction to layers at 100% dolomite. Island nanotopography formed on both Ca‐rich and near‐stoichiometric dolomite. Analyses of reaction products from dolomite synthesis indicates that there are no SFM‐detectable products formed in <10 h. SEM‐detectable products formed in 15 h. X‐ray diffraction (XRD)‐detectable products formed in ≈18 h, and the reaction went to completion in ≈40 h. Based on SFM analyses, the induction period for dolomitization in these experiments accounts for ≈20% of the total reaction time necessary to dolomitize CaCO₃ completely under the experimental conditions used here. Island nano‐ topography is inferred to occur at higher degrees of supersaturation than layer nanotopography for three reasons. First, island nanotopography on synthetic calcite and gypsum forms at higher supersaturations than layer nanotopography. Secondly, island nanotopography formed in solutions with higher degrees of supersaturation with respect to dolomite. Thirdly, the greater surface roughness of a crystal face composed of islands compared with layers indicates that island surfaces have higher surface energy than layer surfaces. Therefore, the stability of island surfaces requires a higher degree of supersaturation. Because islands and layers form under a wide range of conditions, their presence provides broadly applicable criteria for evaluating relative degrees of supersaturation under which ancient dolomite formed. Comparison of synthetic dolomites with natural dolomites demonstrates (1) similar nanotopography on natural and synthetic dolomites and (2) both natural planar and non‐planar dolomite may have island nanotopography.     

Interstitial Sn2+ in synthetic and natural cassiterite crystals

Evidence for the presence of Sn²⁺ in an octahedral interstitial site in synthetic and natural cassiterite (SnO₂) is presented. The absorption and relative absorption spectral peaks measured are similar to ones found in Sn²⁺-doped KI by absorption spectrophotometry and Sn²⁺-doped soda-silica glass by reflection spectroscopy. The estimated quantity of interstitial Sn²⁺ present is found by calculating that needed to balance the uncompensated M³⁺ impurity in substitutional Sn⁴⁺ sites where M³⁺ is mainly Al³⁺ and Fe³⁺. Estimates of the oscillator strengths of three Sn²⁺ bands detected by absorption spectrophotometry in the synthetic crystal are given. The interstitial Sn²⁺ content in synthetic and natural cassiterite is not affected by heating,⁶⁰Co gamma irradiation, or UV light treatment with a high pressure xenon-mercury lamp.     

祖母绿产地鉴别研究综述

祖母绿是一种名贵彩色宝石,其产地来源对祖母绿价值的评定具有重要影响。祖母绿的产地鉴别因而成为宝石实验室的重要技术,也是宝石学领域的研究热点。祖母绿的包裹体、谱学特征和化学成分是常用且关键的产地鉴别信息,但随着祖母绿产地研究数据的积累,传统的产地鉴别方法备受挑战。文章系统整理和归纳分析了全球各产地祖母绿的宝石学特征、包裹体信息、谱学特征和主微量成分数据,在综述前人研究结果的基础上,系统阐明了目前祖母绿产地鉴别的研究现状,总结了不同产地祖母绿的宝石学特征和包裹体特征,划分了紫外-可见光-近红外(UV-VIS-NIR)光谱类型,揭示了各产地祖母绿的成分指纹信息,并以案例的形式阐明区分祖母绿常见重要产地的方法。全球尺度的对比虽然表明不同产地祖母绿包裹体种类多数雷同、光谱趋同、成分含量范围重叠明显,但也从包裹体出现频率、UV-VIS-NIR光谱样式类型、重水吸收样式和成分投图参数的选择上提供了产地鉴别的新思路。综上所述,文章旨在促进祖母绿鉴别技术的发展,为祖母绿的产地溯源提供科学依据。     

Origin of emerald deposits of Brazil

Precambrian emerald deposits of Brazil are found in a typical geologic setting with Archean basement and supracrustal, ultramafic, granitoid and rocks. Volcano-sedimentary series occur as imbricated structures or as bodies affected by complex folding and deformation. Emerald mineralization belongs to the classic biotite-schist deposit, which formed by the reaction of pegmatitic veins within ultrabasic rocks. At the same time, pegmatite-free emerald deposits linked to ductile shear zones are also known. Emerald formation is attributed to infiltrational metasomatic processes provoking a K-metasomatism of the ultrabasic rocks and also a desilication of the pegmatites. A new classification based on the geological setting, structural features, and ore paragenesis is proposed.     

Spectroscopic properties of Cr-doped and Cr,Li-doped synthetic forsterite crystals

Cr-droped and Cr,Li-doped forsterite crystals were grown and their optical properties were investigated. It was shown that when only Cr is doped, Cr³⁺ is substituted at the site of low crystal field, and the energy level ²E lie above the ⁴T₂ level, while ⁴T₂ is just above ²E when Cr and Li are codoped. The difference was rationalized by a deformation of the Cr substituted site with the introduction of Li.     

云南大丫口祖母绿矿床中电气石的地球化学特征及其对成矿的指示意义

祖母绿是由微量Cr和/或V致色的绿色绿柱石.位于云南省麻栗坡县的大丫口祖母绿矿床是中国重要的祖母绿矿床,近年来取得了一系列的研究进展,但与祖母绿相关的电气石的研究工作还未展开.本文以大丫口矿床含祖母绿矿脉和非矿脉中的电气石为研究对象,在详细的野外调查和岩相学研究基础上,对电气石进行成分测试,旨在探讨电气石成因、查明物质...     

澳大利亚孟席斯祖母绿的光谱学特征

采用红外吸收光谱、拉曼光谱、紫外-可见-近红外吸收光谱等无损分析技术,并结合激光诱导击穿光谱和电子探针对澳大利亚孟席斯祖母绿的光谱特征、成分特征和颜色成因进行了研究。红外光谱分析显示孟席斯祖母绿具有[Si_6O_(18)]基团振动特征,其结构孔道中的Ⅱ型水吸收强于Ⅰ型水;拉曼光谱特征峰主要在323 cm、397 cm~(-1)、685 cm~(-1)和1067 cm~(-1),并可检测到142 cm~(-1)和190 cm~(-1)等弱散射峰;紫外-可见-近红外吸收光谱主要由Cr~(3+)、V~(3+)、Fe~(2+)和Fe~(3+)的吸收组成,其中424 nm和611 nm的吸收由Cr~(3+)和V~(3+)联合作用导致,644 nm、661 nm和682 nm的吸收由Cr~(3+)产生。结合Cr_2O_3含量显著高于V_2O_3的化学成分特征,表明孟席斯祖母绿主要由Cr致色。同时将孟席斯祖母绿与云南祖母绿进行对比分析,为孟席斯祖母绿的宝石学鉴定和质量评价提供依据。     

Thermoluminescence, electron paramagnetic resonance and optical absorption in natural and synthetic rhodonite crystals

Thermoluminescence, electron paramagnetic resonance and optical absorption properties of rhodonite, a natural silicate mineral, have been investigated and compared to those of synthetic crystal, pure and doped. The TL peaks grow linearly for radiation dose up to 4 kGy, and then saturate. In all the synthetic samples, 140 and 340°C TL peaks are observed; the difference occurs in their relative intensities, but only 340°C peak grows strongly for high doses. Al₂O₃ and Al₂O₃ + CaO-doped synthetic samples presented several decades intenser TL compared to that of synthetic samples doped with other impurities. A heating rate of 4°C/s has been used in all the TL readings. The EPR spectrum of natural rhodonite mineral has only one huge signal around g = 2.0 with width extending from 1,000 to 6,000 G. This is due to Mn dipolar interaction, a fact proved by numerical calculation based on Van Vleck dipolar broadening expression. The optical absorption spectrum is rich in absorption bands in near-UV, visible and near-IR intervals. Several bands in the region from 540 to 340 nm are interpreted as being due to Mn³⁺ in distorted octahedral environment. A broad and intense band around 1,040 nm is due to Fe²⁺. It decays under heating up to 900°C. At this temperature it is reduced by 80% of its original intensity. The pink, natural rhodonite, heated in air starts becoming black at approximately 600°C.     

The analysis of zoning in magmatic crystals with emphasis on olivine

Many of the observed features of zoning in magmatic phenocrysts may be due to the orientation of the section rather than inherent properties of the crystals. An ideal section for the studying of zoning in magmatic crystals has two characteristics: it goes through the center of the crystal, and is perpendicular to one or more crystal faces. Using a model zoned olivine crystal, it is possible to construct accurate zoning profiles for different types of section (centered, symmetrical and skewed). The probability of obtaining a random section which passes within x% of the center of a crystal is shown to be P=0.0x, while the probability that a random section will be within A degrees of perpendicular to a given plane is P=sin(A). A systematic approach to the study of zoned crystals is outlined. In particular, it is suggested that composition be plotted against distance cubed, in order to correct for the volume versus size problem. A method of determining if a given section goes through (or near) the center of a zoned crystal is also presented. The reasoning in this work applies to other types of magmatic crystals such as pyroxenes and plagioclase.     

世界祖母绿矿床研究现状及存在问题

从祖母绿矿产资源、成矿地质环境与成因、祖母绿的包裹体特征研究及其呈色机理等方面,对当前世界主要祖母绿矿床的研究现状、分类等进行了评述。分析了祖母绿中包裹体的形成及其与成矿环境之间的相关性。同时也对我国的祖母绿矿床作了简要介绍。最后对祖母绿矿床研究中存在的问题提出了一些建议。     

云南麻栗坡祖母绿的矿物学特征研究

利用电子探针、X射线衍射等技术对云南麻栗坡祖母绿进行了矿物学研究,结果表明祖母绿含碱金属和铁镁质两组主要微量元素;V2O3含量明显高于Cr2O3,表明主要是V致色;折射率No=1.584~1.586,Ne=1.576~1.579,相对密度S.G=2.70±0.01;类质同像替代以八面体替代为主。麻栗坡祖母绿的矿物学特征可用于作为产地鉴定的依据。     

Observation of reactions in synthetic Ca-poor pyroxene single crystals at elevated temperatures by X-ray diffraction

Diffuse streaks in diffraction patterns of synthetic pyroxene single crystals at elevated temperatures are used to determine which reactions are initiated and how they proceed. The samples investigated are a) a host orthopyroxene (Wo₄En₈₃Fs₁₃) containing oriented pigeonite (Wo₆En₇₈Fs₁₆) parallel to (100) and b) a pigeonite (Wo₈En₇₅Fs₁₇). The maximum temperatures were 820° C and 1,015° C, respectively. No partial melting occurs at these temperatures, all reactions are in the subsolidus. In case a) augite is formed parallel to the (001) plane of pigeonite, but the augite is not exsolved by the pigeonite. This is proved by the absence of the obligatory streaks between corresponding reflections in highly resolved precession photographs. Instead, there are streaks from augite to the corresponding reflections of the host orthopyroxene. Example b) demonstrates that the temperature of the high-low transformation of pigeonite is very sensitive to the Ca content and clearly depends on the exsolution of augite. This augite is oriented parallel to (100) of pigeonite, not to (001). Both the high and the low pigeonite are present over a range of ～150° C, while the exsolution of augite continues. Simultaneously, orthopyroxene is also formed sharing (100) of pigeonite. There seems to be an indication that only low pigeonite inverts to orthopyroxene.     

Quantitative textural analysis of packings of elongate crystals

The spatial distribution of grains in a solidifying igneous rock controls the physical properties of the crystal mush, and in turn is controlled by the rate of crystal growth and accumulation. A predominant non-spherical habit for igneous minerals brings into question the use of spherical particles in reference packings used for quantification of spatial distribution. Furthermore, variations of crystal clustering/ordering with length scale require spatial statistics which take into account the distribution of particles beyond nearest neighbours. Using random close packings of spherocylinders, we demonstrate the importance of aspect ratio for the aggregation index (usually known as R) and show that packings of spherical particles have more structure than packings of rods. The spatial distribution functions demonstrate that the plagioclase grains in the colonnade from the Holyoke basalt are clustered on a length scale of 0.5 mm. Understanding the controls on grain spatial distribution in igneous rocks will depend on the application of these techniques to well-understood environments.     

Thermal expansion coefficients for indialite,emerald, and beryl

Thermal expansion coefficients ?₁ and ?₃ calculated for the hexagonal minerals indialite, emerald and beryl are, in general, small with ?₃ being negative near room temperature. This unusual behavior leads to low volume coefficients of thermal expansion (β=2?₁+?₃) making these materials ideal ceramic bodies for catalyst carriers in air-pollution control. The temperature at which the c-cell edge length of beryl is a minimum is strongly dependent upon the presence of trace amounts of impurity atoms. This effect is ascribed to changes in the Grüneisen parameters.     

Statistical inverse analysis based on genetic algorithm and principal component analysis: Method and developments using synthetic data

This study concerns the identification of parameters of soil constitutive models from geotechnical measurements by inverse analysis. To deal with the non‐uniqueness of the solution, the inverse analysis is based on a genetic algorithm (GA) optimization process. For a given uncertainty on the measurements, the GA identifies a set of solutions. A statistical method based on a principal component analysis (PCA) is, then, proposed to evaluate the representativeness of this set. It is shown that this representativeness is controlled by the GA population size for which an optimal value can be defined. The PCA also gives a first‐order approximation of the solution set of the inverse problem as an ellipsoid. These developments are first made on a synthetic excavation problem and on a pressuremeter test. Some experimental applications are, then, studied in a companion paper, to show the reliability of the method. Copyright © 2009 John Wiley & Sons, Ltd.     

Oxygen isotope systematics of emerald: relevance for its origin and geological significance

Oxygen isotopic composition of emerald from 62 occurrences and deposits in the world reveals a wide range in δ¹⁸O (SMOW) between +6.2 and +24.7‰. The δ¹⁸O-values for each deposit are restricted and can be used to determine the origin of emerald from the world's most important producers. The δ¹⁸O-value of emerald appears to be a fingerprint of its origin, especially for gems of exceptional quality from Colombia (eastern emerald zone, δ¹⁸O = +16.8 ± 0.1‰; western emerald zone, δ¹⁸O = +21.2 ± 0.5‰), Afghanistan (δ¹⁸O = +13.5 ± 0.1‰), Pakistan (Swat-Mingora districts, δ¹⁸O = +15.7 ± 0.1‰), Brazil (Santa Terezinha de Goiás, δ¹⁸O = +12.2 ± 0.1‰; Quadrilatero Ferrifero, δ¹⁸O = +6.9 ± 0.4‰) and Zimbabwe (Sandawana, δ¹⁸O = +7.5 ± 0.5‰). Furthermore, the ¹⁸O-composition of emerald appears to be a good marker of its geological environment because the data suggest that host-rock-buffering of fluid δ¹⁸O is considerable during fluid-rock interaction. Received: 29 January 1998 / Accepted: 25 March 1998     

Soil moisture response to white ash mortality following emerald ash borer invasion

Emerald ash borer (EAB) (Agrilus planipennis Fairmaire), an invasive forest insect first identified in southeastern Michigan in 2002, is established in at least 32 US states and three Canadian provinces. Ash (Fraxinus spp.) mortality rates in some forested areas exceed 90%, but to date, little is known about the potential effects of EAB-caused ash mortality on hydrological processes. More broadly, there is a need for information on the timing and magnitude of soil moisture response to species-specific mortality of overstory vegetation in deciduous forest systems. Soil moisture was examined in 28 forested sites where 0–100% of the white ash basal area (Fraxinus americana L.) was killed by EAB. Synoptic measurements of near-surface (0–6 cm depth) soil moisture were collected from 112 plots (18 m radius) within the sites. Three plots were also instrumented with soil moisture sensors at 10 and 25 cm depth to log hourly measurements from May to October. Synoptic data showing white ash mortality and soil moisture were positively correlated in the 34 plots with ≥?5% mortality (by total basal area). In the intensively monitored plots, volumetric soil moisture declined from 37 to 16% between July and September where white ash mortality was low (0.6% of basal area killed), but remained near field capacity (~?30%) throughout the monitoring period in the high mortality plot (8.6% of basal area killed), meriting further investigation to assess effects of white ash mortality on evapotranspiration and soil moisture dynamics in heterogeneous upland forests. Altered soil moisture may have implications for regrowth dynamics, infiltration/runoff partitioning, and nutrient cycling, but additional study to quantify the extent and duration of EAB-related ash mortality on hydrology at the plot and watershed scale is necessary.