基于丹磺酰基团的高选择性的铜离子荧光离子探针

设计合成了含有丹磺酰基团的铜离子荧光探针a,该探针在水溶液中(含有1%的DMSO)对铜离子识别和检测具有较高的灵敏度和选择性。该识别是以丹磺酰基团的荧光发射的蓝移和微弱猝灭为响应信号,并且对其它碱金属和碱土金属离子(如K+、Na+、Mg2+、Ca2+等)以及过渡金属离子Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Zn2+、Cd2+、和Ag+等都没有识别响应。     

Features of metamict zircons based on their micrographs and the data of electron microprobe analysis

A new quantitative approach on the basis of joint probability distribution (JPD) analysis of BSE- and CL-images is proposed for studies of the zoning of polygenic (polychronous) grains of zircon. It was shown for the example of zircon of the Mugodzhar metamorphic rocks (South Ural) that a series of zones might be distinguished in the grains of high chemical (structural) heterogeneity. Zones Ia and Ib belong to the fragments of crystalline and radiation-damaged zircon, respectively. Zone II corresponds to the primarily disordered areas (the “genetically metamict” zones) of high concentrations of the impurities of Y, P, REE, U, Hf, etc. The Ia-Ic trend is related to the process of autoradiation metamictization. Based on the data on oxygen content, the declinations of zircon composition from the stoichiometry and the hydration effects were considered.     

Infrared and electron microprobe analysis of tourmalines

Infrared and electron microprobe analysis of natural tourmalines from the dravite-schorl and elbaite-schorl series were carried out. The infrared study differentiates between OH groups located at the centre of hexagonal rings and those which are placed between hexagonal pillars and are coordinated to two Al ions. The correlation of infrared spectra with chemical composition of tourmalines made possible the assignment of different OH stretching bands to the more frequent octahedral cation associations. The study of the thermal dehydroxylation of tourmalines in air indentified the IR bands corresponding to OH bonded to Fe⁺² ions in AlAlFe, AlFeLi or FeFeFe environments. The change in intensity of the OH absorption lines with the sample orientation has permitted the identification of several orientations of the OH bond axes. Electron microprobe analysis of zoned coloured samples has shown that the Fe, Mn distribution is partially ordered in some samples of the elbaite-schorl series.     

Petrographic and electron microprobe study of the Monturaqui impactite

Cindery, glassy impactites from the Monturaqui meteorite crater contain unshocked and shocked mineral and rock fragments together with Ni-Fe-Co-P spherules tightly bound in a partly devitrified matrix of clear, green or brown glass. Shock effects range from lightly shocked (100 kb) to intensely shocked (650 kb).Electron microprobe analyses of the metal spherules show that composition is related to grain size, the smallest (2–10 ) spherules being highest in Ni, the largest spherules (0.4 to 1.5 mm) being lowest in Ni. The lowest Ni content of analyzed spherules is 7.8 wt %, which suggests that the original meteorite may have been an octahedrite. Analysis of the mixed matrix glasses indicates extreme compositional differences compared to granite country rock.A series of high-temperature heating experiments, using various heating and cooling rates and atmospheric conditions were conducted to simulate the effects observed in the impactites. Results suggest that (a) higher Ni content in smaller spherules resulted from residual concentration after preferential melting at temperatures greater than 1400° C and oxidation of Fe; and (b) mixed matrix glasses that are low in SiO₂ and high in FeO resulted from preferential melting of lower melting components of the granite at temperatures greater than 1300° C under rapid heating and cooling conditions, together with contamination by Fe, Ni and Co from the meteorite. In addition, Fe enrichment in glasses that surround the larger spherules depends essentially on the amount of oxidation prior to and during incorporation of the spherules into the glass matrix.     

电子探针与扫描电镜在翡翠饰品鉴别中的应用

利用电子探针、扫描电子显微镜对翡翠饰品进行表面形貌、物质组成的测定,结合偏光显微镜研究成果,以其微区、微量、无损、快速的特点,为翡翠饰品的鉴别提供了一种有效的方法和途径.     

Estimation of Fe3+ from electron microprobe analyses: observations on calcic amphibole and chlorite

ABSTRACT Metabasites and metagreywackes from the Pelona and Rand Schists of southern California were analysed using three different electron microprobes. For all three instruments, the estimated Fe³⁺ contents of calcic amphibole, chlorite and epidote are positively correlated. For some samples, there is an additional correlation between high estimated Fe³⁺ and the presence of magnetite. These results imply that microprobe analyses can be used to discern relative differences in Fe³⁺. However, microprobe data and calculations on the sensitivity of the correction procedures to systematic analytical errors indicate that estimated values of Fe³⁺ are not significant in an absolute sense. Thus, estimates of Fe³⁺ are meaningful when comparing samples analysed with a single microprobe, but must be used with caution when comparing analyses obtained on more than one probe.     

An electron microprobe study of some Alberta placer gold

Summary The detailed characteristics of 435 placer gold grains from the North Saskatchewan and Athabasca rivers have been investigated using a combination of optical microscopy, energy dispersive electron microprobe analysis and SEM techniques. Most grains show high-fineness rims surrounding lower-fineness cores (giving an extreme range of 4.3%–46.1% Ag within an individual grain). Characteristics of the rims lend support to the hypothesis that they are the products ofin situ leaching of silver followed by transport which largely destroys a spongy texture produced by the leaching. There is no change in the average Ag content of grains of any given size range with distance downstream, which also indicates that all significant leaching takes place before transportation. However, differences are apparent in the average Ag content with grain size.The clustering about certain values of fineness of the nuclei of grains which is seen in samples from both rivers, suggests that Au was largely derived from specific sources in the mountains (Omineca geanticline) to the west rather than redistributed from Shield localities during glaciation.

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Mikrosonden-Untersuchungen an Seifengold aus Alberta, Kanada

Zusammenfassung 435 Körner aus Goldseifen im North Saskatchewan und im Athabasca-Fluß wurden einer detaillierten Untersuchung mit optischer Mikroskopie, energie-dispersiver Mikrosondenanalytik und Rasterelektronenmikroskopie unterzogen.In den meisten Körnern umgibt ein Rand mit hohem Feinheitsgrad einen Kern mit niedrigem Feinheitsgrad (dies führt zu beträchtlichen Schwankungen des Ag-Gehaltes innerhalb des einzelnen Kornes; im Extremfall 4,3%–46,1% Ag). Die Charakteristik der Ränder gibt Anlaß zu der Hypothese, daß das Silber dieser Ränder in situ herausgelöst worden ist, bevor die Körmer transportiert wurden; die während des Transportes auf die Körner einwirkenden Kräfte haben dann die poröse Textur, die durch das herauslösen des Silbers entstanden waren, weitgehend zerstört. Es findet sich keine Änderung des durchschnittlichen Ag-Gehaltes mit zunehmender Transportweite flußabwärts, solange nur Kömer aus einem Größenintervall betrachtet werden. Dies deutet ebenfalls darauf hin, daß der überwiegende Teil des Silbers vor dem Transport herausgelöst wurde. Man findet jedoch Unterschiede im durchschnittlichen Ag-Gehalt zwischen Körnern verschiedener Größe.Das Auftreten von mehreren bestimmten Werten-Clustern der Feinheitsgrade, die in Proben aus beiden Flüssen zu finden ist, legt nahe, daß Au zum größten Teil aus mehreren, spezifischen Ursprungsgesteinen in den westlich gelegenen Gebirgen (Omineca Geanticline) stammt. Eine glazigene Umverteilung von Gold aus verschiedenen Lokalitäten des Kanadischen Schildes erscheint weniger realistisch.

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With 9 Figures     

Rare minerals of the spinel group in ultrabasites from Bulgaria

Summary Chromite mineralization was found during a detailed geological mapping, carried out in 1962, in the region of the Seven Lakes, Northern Rila Mountain. Mineralogical studies showed that the ore minerals of this mineralization are of a great variety, and are members of the little known group of ferrospinels with varying chromium-, aluminium- and magnesium-content. Only three minerals are described in the present paper. They are well defined varieties, differing from one another by their chemical composition and physical properties.

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Seltene Vertreter der Spinell-Gruppe in Ultrabasiten von Bulgarien

Zusammenfassung Bei einer detaillierten geologischen Kartierung im Gebiet der Sieben Seen, nördliches Rila-Gebirge, wurden im Jahre 1962 Chromit-Mineralisationen gefunden. Die mineralogische Bearbeitung zeigte, daß die Erzminerale dieser Mineralisation stark variieren und daß sie zu der noch wenig bekannten Gruppe der Ferrospinelle mit wechselndem Chrom-, Aluminium- und Magnesiumgehalt gehören. In der vorliegenden Arbeit werden nur drei Glieder beschrieben. Es handelt sich um gut definierte Varietäten, die sich in der chemischen Zusammensetzung und in den physikalischen Eigenschaften unterscheiden.

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With 6 Figures     

Semi-quantitative ion microprobe mass analyses of mineral-rich particles from the upper freeport coal

An ion microprobe mass analyzer (IMMA) has been used to analyze semi-quantitatively mineral-rich coal particles from two separate facies of the Upper Freeport coal bed. Accuracy is estimated to be ? 20% for those elements making up more than 0.1 wt.% of the particles and ? 50% for elements making up less than 0.1 wt.%. Using IMMA data, we found statistically significant differences between the two samples for five (Fe, Ca, Mn, Li, Ce) of the 25 elements detected. For Li and Mn the differences between the mineral-rich particles within samples were similar to differences found between samples on a whole-coal basis. For Ca and Fe, the differences are attributed to different modes of occurrence, and for Ce, the differences are probably due to an irregular distribution of an inorganic phase. We conclude that the IMMA can be used to obtain semi-quantitative data that may provide insight into the distribution and mode of occurrence of some of the elements in coal.     

Petrogenesis of the Apollo 14 high-alumina basalts: Implications from ion microprobe analyses

In this study, ion microprobe analyses of individual minerals are used to investigate the petrogenesis of the Apollo 14 high-Al basalts. We use trace element concentrations from individual minerals in the Apollo 14 high-Al basalts to evaluate both endogenic and exogenic models. The data show that if the Apollo 14 high-Al basalts were produced by melting within the lunar mantle, these basalts cannot be related to one another by closed-system fractional crystallization of a single basaltic melt. Rather, the trace element data show that variable amounts of a KREEP component were added to the basalts by either assimilation, mixing into mantle sources, or impact melting. Single-stage assimilation-fractional crystallization models can only explain the data from this study if an excessively large mass of urKREEP is assimilated into the parent magma before olivine crystallization. Alternatively, the trace element data can be explained if the Apollo 14 high-Al basalts were produced by melting multiple Al-rich mantle sources that contain different amounts of urKREEP. Finally, for impact melting to be a relevant process, the data require that multiple large impact melts be formed from mixed KREEP-rich target lithologies. The resulting impact melts must then crystallize to produce basalts with igneous textures, high Al₂O₃ concentrations, uniform major element compositions, and a wide range of incompatible trace element concentrations.     

A sample fusion technique for whole rock analysis with the electron microprobe

A technique has been devised for major element whole rock analysis using the electron microprobe. Rock powders are fused on a strip heater using a low voltage, high amperage source and quenched to form a glass bead in a container pressurized with argon. Sample weights of 20 mg to ~ 300 μg with run times of 20–60 sec produce sufficient material for analysis. Analyses of the fused samples compare favorably with those achieved by X-ray fluorescence and neutron activation for major elements in a wide range of silicate rock compositions. Analytical errors for major element concentrations are generally 5% or less. Alkali losses for Rb are ~10% at the 20 ppm level as determined by isotope dilution mass spectrometry. Sodium determinations compare favorably with those obtained by neutron activation analysis.     

Nickel geochemistry of a Philippine laterite examined by bulk and microprobe synchrotron analyses

The Ni geochemistry of limonite and saprolite laterite ores from Pujada in the Philippines has been investigated using a mixture of laboratory and synchrotron techniques. Nickel laterite profiles are typically composed of complicated mineral assemblages, with Ni being distributed heterogeneously at the micron scale, and thus a high degree of spatial resolution is required for analysis. This study represents the first such analysis of Philippine laterite ores. Synchrotron bulk and microprobe X-ray absorption spectroscopy (XAS), comprising both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, together with synchrotron microprobe X-ray fluorescence microscopy (XFM) and diffraction (XRD) have been applied to provide quantitative analysis of the mineral components and Ni speciation.Synchrotron microprobe EXAFS spectroscopy suggests that the limonite Ni is associated with phyllomanganate via adsorption onto the Mn oxide layers and substitution for Mn within these layers. Laboratory scanning electron microscopy, coupled to electron dispersive spectroscopy analyses, indicates that Ni is also associated with concentrated Fe containing particles and this is further confirmed by synchrotron bulk and microprobe investigation. Linear combination fitting of the bulk EXAFS limonite data suggests 60 ± 15% of the Ni is associated with phyllomanganate, with the predominant fraction adsorbed above vacancies in the MnO₆ layers with the remainder being substituted for Mn within these layers. The remaining 40 ± 10% of the Ni in the limonite ore is incorporated into goethite through replacement of the Fe. In the saprolite ore, 90 ± 23% of the Ni is associated with a serpentine mineral, most likely lizardite, as a replacement for Mg. The remaining Ni is found within phyllomanganate adsorbed above vacancies in the MnO₆ layers.     

电子探针化学测年法在晶质铀矿/沥青铀矿定年研究中的应用现状

简要介绍近年发展起来的各种微区测年方法及其优缺点,重点介绍不同时期电子探针化学测年法在晶质铀矿/沥青铀矿定年研究中的发展状况及前人使用的分析测试条件,并展望了该方法在晶质铀矿/沥青铀矿定年研究中的应用前景及可能存在的问题。通过系统研究,认为该方法在铀矿物定年研究中将大有作为,尤其是在微小铀矿物（〈10μm）和多期次、多阶段铀矿体的微区定年研究中更能显示其优越性。     

Heat-producing elements in the lunar mantle: Insights from ion microprobe analyses of lunar pyroclastic glasses

We provide new estimates for the abundance of heat-producing elements in the lunar mantle by using SIMS techniques to measure the concentrations of thorium and samarium in lunar pyroclastic glasses. Lunar pyroclastic glasses are utilized in this study because they represent quenched products of near-primary melts from the lunar mantle and as such, they provide compositional information about the mantle itself. Thorium and samarium were measured because: (1) Th is not significantly fractionated from Sm during partial melting of the pyroclastic glass source regions, which are dominated by olivine and pyroxene. Therefore, the Th/Sm ratios that we measure in the pyroclastic glasses reflect the Th/Sm ratio of the pyroclastic glass source regions. (2) Strong correlations between Th, U, and K on the Moon allow us to use measured Th concentrations to estimate the concentrations of U and K in the pyroclastic glasses. (3) Th, Sm, U, and K are radioactive elements and as such, their concentrations can be used to investigate heat production in the lunar mantle.The results from this study show that the lunar mantle is heterogeneous with respect to heat-producing elements and that there is evidence for mixing of a KREEP component into the source regions of some of the pyroclastic glasses. Because the source regions for many of the glasses are deep (?400 km), we propose that a KREEP component was transported to the deep lunar mantle. KREEP enriched sources produce 138% more heat than sources that do not contain KREEP and therefore, could have provided a source of heat for extended periods of nearside basaltic magmatism. Data from this study, in conjunction with models for the fractional crystallization of a lunar magma ocean, are used to show that the average lunar mantle contains 0.15 ppm Th, 0.54 ppm Sm, 0.039 ppm U, and 212 ppm K. This is a greater enrichment in radiogenic elements than some earlier estimates, suggesting a more prolonged impact of radiogenic heat on nearside basaltic volcanism.     

The phenomenon of deficient electron microprobe totals in radiation-damaged and altered zircon

The phenomenon of deficient electron microprobe analyses, with sums of analyzed constituents often below 95 wt%, is assigned to the analysis of altered, porous minerals. With the example of three zircon populations we show that low totals are related to textural features (i.e., numerous pores of tens to hundreds of nanometers size) as well as to the chemical composition (i.e., water content well within the wt% range, which may affect partial sample degradation under the electron beam). The formation of the spongy texture is explained by the alteration of a previously radiation-damaged and, thus, volume-expanded material in a fluid-driven replacement reaction. The smaller volume of the reaction product (crystalline, non volume-expanded zircon) accounts for the formation of numerous voids and pores, which are perfect candidates for the incorporation of water. The alteration has also resulted in uptake of non-formula elements such as Al, P, Ca, Fe, Y, and REEs whereas Si and Zr are depleted. In one case, strong uptake of non-radiogenic Pb in altered zircon was observed. Because porous, low-total zircon has formed in secondary alteration process, its occurrence can be considered as an indicator of a secondary alteration history of the host rock. Low-total zircon is easily recognized by very low electron back-scatter intensities, which are closely related to the two main causes of the analytical shortfall (i.e., water content and porosity) and often lowered furthermore by the presence of light non-formula elements (especially P and Fe) up to the wt% range.     

Petrogenesis of the Eppawala carbonatites, Sri Lanka: A cathodoluminescence and electron microprobe study

Field and petrographic investigations, cathodoluminescence (CL) studies as well as microprobe analyses of major rock-forming minerals were conducted to establish the crystallization processes in the Eppawala carbonatites, Sri Lanka. The well preserved magmatic textures and crystal morphologies combined with the chemistry of apatite, calcite and dolomite indicate two major stages of crystal growth, which were accompanied by dynamic crystallization conditions. Initially, nucleation of apatite, ilmenite and possibly olivine was associated with rapid crystal growth during slow cooling of the carbonatite melt at depth. The heat loss through the roof and crystallization processes induced the development of turbulent convective currents, which in turn prevented further nucleation and growth of crystals and led to the dispersion of these earlier formed crystals within the magma chamber. Then, rapid upward movement of magma along structural weaknesses led to (i) the transport of mineral clusters, (ii) deformation of ilmenite, (iii) fracturing of apatite and (iv) the emplacement of the carbonatite melt as dykes. Here, the conditions were favourable for the simultaneous crystallization of magnetite, calcite and dolomite in a non-turbulent environment. Subsequent subsolidus alteration caused the hydrothermal overprint of the documented mineral assemblages, particularly along grain boundaries. The study demonstrates that detailed textural examinations of carbonatites combined with mineral chemical analyses and CL investigations can reveal the crystallization processes within carbonatite melts.     

Geochronological constraints on the evolution of high-pressure felsic granulites from an integrated electron microprobe and ID-TIMS geochemical study

A combined geochronological, geochemical, and Nd isotopic study of felsic high-pressure granulites from the Snowbird Tectonic Zone, northern Saskatchewan, Canada, has been carried out through the application of integrated electron microprobe and isotope dilution thermal ionization mass spectrometry (ID-TIMS) techniques. The terrane investigated is a 400 km² domain of garnet–kyanite–K–feldspar-bearing quartzofeldspathic gneisses. Monazite in these granulites preserves a complex growth history from 2.6 to 1.9 Ga, with well-armored, high Y and Th grains included in garnet yielding the oldest U–Pb dates at 2.62 to 2.59 Ga. In contrast, matrix grains and inclusions in garnet rims that are not well-armored are depleted in Y and Th, and display more complicated U–Pb systematics with multiple age domains ranging from 2.5 to 2.0 Ga. 1.9 Ga monazite occurs exclusively as matrix grains. Zircon is typically younger (2.58 to 2.55 Ga) than the oldest monazite. Sm–Nd isotope analysis of single monazite grains and whole rock samples indicate that inclusions of Archean monazite in garnet are similar in isotopic composition to the whole rock signature with a limited range of slightly negative initial _Nd. In contrast, grains that contain a Paleoproterozoic component show more positive initial _Nd, most simply interpreted as reflecting derivation from a source involving consumption of garnet and general depletion of HREE's. Our preferred interpretation is that the oldest monazite dates record igneous crystallization of the protolith. The ca. 2.55 Ga dates in zircon and monazite record an extensive melting event during which garnet and ternary feldspar formed. Very high-pressure (> 1.5 GPa) metamorphism during the Paleoproterozoic at 1.9 Ga produced kyanite from garnet breakdown, and resulted in limited growth of new monazite and zircon. In the case of monazite, this is likely due to the armoring and sequestration of early-formed monazite such that it could not participate in metamorphic reactions during the high-pressure event, as well as the depletion of the REE's due to melt loss following the early melting event.     

Sarma‐based key‐group method for rock slope reliability analyses

The methods used in conducting static stability analyses have remained pertinent to this day for reasons of both simplicity and speed of execution. The most well‐known of these methods for purposes of stability analysis of fractured rock masses is the key‐block method (KBM). This paper proposes an extension to the KBM, called the ‘key‐group method’ (KGM), which combines not only individual key‐blocks but also groups of collapsable blocks into an iterative and progressive analysis of the stability of discontinuous rock slopes. To take intra‐group forces into account, the Sarma method has been implemented within the KGM in order to generate a Sarma‐based KGM, abbreviated ‘SKGM’. We will discuss herein the hypothesis behind this new method, details regarding its implementation, and validation through comparison with results obtained from the distinct element method. Furthermore, as an alternative to deterministic methods, reliability analyses or probabilistic analyses have been proposed to take account of the uncertainty in analytical parameters and models. The FOSM and ASM probabilistic methods could be implemented within the KGM and SKGM framework in order to take account of the uncertainty due to physical and mechanical data (density, cohesion and angle of friction). We will then show how such reliability analyses can be introduced into SKGM to give rise to the probabilistic SKGM (PSKGM) and how it can be used for rock slope reliability analyses. Copyright © 2005 John Wiley & Sons, Ltd.     

含超轻元素Be矿物的电子探针定量分析——测试条件的约束

铍（Be）是战略性资源,属于关键金属。Be在电子探针（EMPA）可分析的元素范围内属于最难测准的一个元素。难测准的原因在于Be属于超轻元素,其特征X-射线不但信号弱、能量低,而且易受其他元素强烈吸收效应的影响,因此硬件上需要EMPA配置大面网间距的特殊分光晶体。而不同厂家不同大面网间距分光晶体配置的EMPA在铍矿物的测试条件存在明显差异,即使同一EMPA测试不同Be矿物分析条件也不一致。尤其是占据国内市场主流的JEOL电子探针目前也只尝试分析过绿柱石一种Be的矿物。本文利用配置LDE3H分光晶体的JXA-8100（JEOL）电子探针,对除绿柱石之外的金绿宝石、硅铍石、硼铍石和锌日光榴石四种Be矿物开展了Be等元素最佳定量分析方法的研发。通过不同铍矿物的全元素扫描,发现与CAMECA电子探针不同,JEOL电子探针不存在Be_Kα峰被Si_L2,3,M1峰干扰问题。同时发现每种含Be矿物Be_Kα峰位存在不同程度的漂移现象,并结合原子轨道杂化及吸收效应等理论对该现象进行了合理的解释。在此基础上,建立起配置LDE3H分光晶体的JEOL电子探针定量分析金绿宝石、硅铍石、硼铍石和锌日光榴石不同Be矿物中Be等元素含量的有效方法。该Be矿物原位分析方法的探索,不仅为JEOL EMPA用户提供Be矿物分析的成熟经验,也必将为铍资源的相关研究和找矿勘查提供有力的技术支撑。