光石沟晶质铀矿:一种潜在的铀矿物电子探针定量分析标准样品

电子探针定量分析是采用元素A在待测样品中的特征X射线强度与标准样品中元素A特征X射线强度相比较而进行的,要实现未知样品的元素定量分析必须要具有相应的标准样品,目前可用于铀元素分析的电子探针分析标准样品极少,且缺乏与天然矿物成分、结构近似的标准样品。国际和国内已经制定了电子探针标准物质研制的规范(GB/T 4930—2008/ISO14595:2003),按该规范规定的方法研究了产于陕西光石沟铀矿床的晶质铀矿,结果表明:这些晶质铀矿晶形发育好,颗粒大,具备良好的纯度、均匀性和稳定性。随机选择30个颗粒进行均匀性检测,UO₂和PbO在95%的置信区间的平均浓度不确定度分别为0.275%和0.060%,具备非常好的均匀性;该晶质铀矿在电子探针电子束长时间(如360s)轰击下和在自然条件下存放,均具有良好的稳定性;采用五家实验室化学分析定值方法确定了该晶质铀矿的化学成分,并计算了不确定度,主量元素UO₂为(86.80±0.36)%,PbO为(4.80±0.07)%,其他元素也给出了参考值。综合以上研究结果:产于光石沟铀矿床的晶质铀矿满足GB/T 4930—2008关于电子探针定量分析标准样品的各项判据,是一个潜在的适用于铀矿物化学成分电子探针定量分析使用的天然矿物标准样品。     

Potential Orthopyroxene,Clinopyroxene and Olivine Reference Materials for In Situ Lithium Isotope Determination

Over 1400 electron probe and 700 ion probe microanalyses were performed on eleven mineral separates to evaluate their potential as reference materials for in situ Li isotopic determination. Our results suggest the homogenous distributions of major elements, Li and its isotopes for each sample. Hence, these samples are suitable to be used as reference materials for in situ measurements of Li abundance and Li isotopes by secondary ion mass spectrometry (SIMS) or laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). These samples have the advantage of mitigating probable matrix effects during calibration owing to the wide range of compositions. The effect of composition on the δ⁷Li of olivine measured by SIMS is a linear function of composition, with δ⁷Li increasing by 1.0‰ for each mole per cent decrease in forsterite component.     

LA-ICP-MS微区原位准确分析含水硅酸盐矿物主量和微量元素

通过描述一种利用LA-ICP-MS准确测定含水硅酸盐矿物主量元素和微量元素含量的多外标、无内标分析方法.总结出该方法基于矿物化学计量式计算含水硅酸盐矿物中挥发分的相对含量,再将全部分析元素归一化到总金属氧化物含量(100%减含水量)的原理,利用多种天然成分的岩石标准玻璃(如MPI-DING玻璃和USGS玻璃)作为外标进行校正计算.利用该方法对角闪石、绿帘石、电气石和透闪石等含水硅酸盐矿物进行了分析,并与利用电子探针和微钻(直径300 μm)取样溶液-ICP-MS分析的结果进行了对比研究.研究结果表明:对于组成均一的主量元素的分析结果与电子探针分析数据一致,相对偏差集中在5%以内.除了那些分布异常不均一的元素(在300 μm尺度上),对微量元素的分析结果与溶液-ICP-MS分析结果具有很好的一致性,二者之间的相对偏差大部分集中在10%以内.研究结论为采用归一化校正策略,选择MPI-DING和USGS玻璃作为外标,利用LA-ICP-MS微区分析方法可以准确测定含水硅酸盐矿物中的主、微量元素含量.      

Determination of Thorium-230 in CCRMP Reference Samples by Alpha Spectroscopy

Thorium-230 concentrations have been determined in 11 CCRMP (Canadian Certified Reference Materials Project) reference rock and ore samples using alpha spectroscopy following a chemical separation of the thorium. Literature data are available for only one of these 11 reference samples.     

1988 COMPILATION REPORT ON TRACE ELEMENTS IN SIX ANRT ROCK REFERENCE SAMPLES: DIORITE DR-N, SERPENTINE UB-N, BAUXITE BX-N, DISTHENE DT-N, GRANITE GS-N AND POTASH FELDSPAR FK-N

The six ANRT rock reference samples (DR-N, UB-N, BX-N, DT-N, GS-N, FK-N) have been distributed as reference samples for nearly twenty years. All available data on trace elements in these samples are presented and evaluated. It has been possible to assign working values for nearly 40 trace elements. These samples prepared in 600 to 1300 kg quantities are expected to last for some decades to come.     

Compilation Report (1966–1987) on Trace Elements in five CRPG Geochemical Reference Samples: Basalt BR; Granites, GA and GH; Micas, Biotite Mica-Fe and Phlogopite Mica-Mg

The five CRPG geochemical reference samples (BR, GA, GH, Mica-Fe and Mica-Mg) have been distributed as reference samples for more than twenty years. All data on trace elements in these samples available to the authors since their first reports have been compiled and evaluated. It has been possible to assign working values for more than forty elements in BR, GA, GH and Mica-Fe and for twenty-three elements in Mica-Mg. The samples are expected to last for another twenty years.     

Natural Obsidian Glass as an External Accuracy Reference Material in Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Compared with solution ICP‐MS, LA‐ICP‐MS studies have thus far reported comparatively few external reference data for accuracy estimates of experiments. This is largely the result of a paucity of available reference materials of natural composition. Here, we report an evaluation of natural glass (obsidian) as an inexpensive and widely available external reference material. The homogeneity of over forty elements in six different obsidian samples was assessed by LA‐ICP‐MS. Accuracy was tested with two obsidian samples that were fully characterised by electron probe microanalysis and solution ICP‐MS. Laser ablation experiments were performed with a variety of ablation parameters (fluence, spot sizes, ablation repetition rates) and calibration approaches (natural vs. synthetic reference materials, and different internal standard elements) to determine the best practice for obsidian analysis. Furthermore, the samples were analysed using two different laser wavelengths (193 nm and 213 nm) to compare the effect of potential ablation‐related phenomena (e.g., fractionation). Our data indicate that ablation with fluences larger than 6 J cm^?2 and repetition rates of 5 or 10 Hz resulted in the most accurate results. Furthermore, synthetic NIST SRM 611 and 612 glasses worked better as reference materials compared with lower SiO₂ content reference materials (e.g., BHVO‐2G or GOR128‐G). The very similar SiO₂ content of the NIST SRM glasses and obsidian (i.e., matrix and compositional match) seems to be the first‐order control on the ablation behaviour and, hence, the accuracy of the data. The use of different internal standard elements for the quantification of the obsidian data showed that Si and Na yielded accurate results for most elements. Nevertheless, for the analysis of samples with high SiO₂ concentrations, it is recommended to use Si as the internal standard because it can be more precisely determined by electron probe microanalysis. At the scale of typical LA analyses, the six obsidian samples proved to be surprisingly homogenous. Analyses with a spot size of 80 μm resulted in relative standard deviations (% RSD) better than 8% for all but the most depleted elements (e.g., Sc, V, Ni, Cr, Cu, Cd) in these evolved glasses. The combined characteristics render obsidian a suitable, inexpensive and widely available, external quality‐control material in LA‐ICP‐MS analysis for many applications. Moreover, obsidian glass is suited for tuning purposes, and well‐characterised obsidian could even be used as a matrix‐matched reference material for a considerable number of elements in studies of samples with high SiO₂ contents.     

Electron Probe Microanalysis of Environmental Samples: Preparation of Reference Materials, Correction for Particle Size Effects and Representative Results on Sediments Recovered from Snow, Power Station Fly Ash and Bone Samples

In this paper we report the results of electron probe X-ray microanalysis (EPMA) that was used to study environmental materials. The mode of preparation and certification of reference samples based on a basaltic glass matrix for environmental applications of EPMA is described. These samples were prepared containing scandium, strontium and barium (from 0.03 up to 7% m/m) and an evaluation was made of homogeneity, their stability to local heating, followed by analysis by independent methods for certification of composition. Matrix correction procedures for the EPMA technique have been developed for particles having a size commensurable with the volume of X-ray generation. An analytical equation for the size factor is proposed and two techniques for selecting optimum conditions for the analysis of environmental samples by EPMA are reported. These procedures provided satisfactory results when utilized in analysing sediments recovered from snow, coal fly ash and the bones of animals and fish, results from which can be used as indicators for evaluating the pollution level of the lower atmosphere, surface and ground water, as well as revealing pollution mechanisms.     

Mineralogical investigations in the interpretation of heavy-mineral geochemical results from till

Heavy-mineral geochemistry and its use in prospecting are based on the fact that some ore minerals (e.g. cassiterite, scheelite, wolframite, chromite, pyrochlore and columbite-tantalite) have a higher specific gravity than the common rock-forming silicates and are highly resistant to weathering in the secondary environment. Till, the most common type of surficial deposit in Finland, is relatively homogeneous and thus constitutes an appropriate sampling material for heavy-mineral geochemical studies. This is especially true in reconnaissance prospecting.The present work concentrates on the interpretation of heavy-mineral anomalies by reference to mineralogical and mineral chemistry data. Tetrabromoethane and a Frantz Isodynamic Separator were used to divide the heavy-mineral samples into subfractions, after which the minerals present were identified by light microscopy, scanning electron microscopy combined with energy-dispersive X-ray spectrometry, electron microprobe techniques and X-ray diffraction.Applications of the methods at three tin anomaly sites in southern Finland are described. The results successfully predicted the presence of a greisen in one area and a pegmatite in another. Those for the third area were somewhat contradictory, the mineralogical composition of the samples suggesting a greisen source for the tin while the composition of the cassiterite pointed to a pegmatite or granite source.     

Sub-Micrometre Resolution FIB-SEM-based ToF-SIMS Used to Map Geochemical Zoning in Four Zircon Reference Materials

Zircon geochemistry can vary over micrometre scales; therefore, natural reference materials need to be well characterised before being used to calculate trace element mass fractions in unmeasured samples. Moreover, reference material homogeneity needs to be ensured with the accelerating rate of geoanalytical developments to map mineral chemistry at increasingly finer scales. Here, we investigate trace element zoning in four widely used zircon reference materials: 91500, Mud Tank, Temora and Plešovice, as well as zircon crystals from the Mount Dromedary/Gulaga Igneous Complex, Australia. Sub-micrometre resolution focused ion beam scanning electron microscope (FIB-SEM) based time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 5 μm resolution LA-ICP-MS mapping show that trace elements are zoned in all reference materials, though 91500 exhibited the least zonation. We demonstrate that FIB-SEM-based ToF-SIMS can rapidly resolve variations in trace elements (e.g., U, Th, Sc, Y, Gd, Dy, Yb and Li) at sensitivities down to the μg g^-1 level with a spatial resolution of 195 nm for areas 100 × 85 μm to 959 × 828 μm. Zircon 91500 is recommended for future quantitative analyses provided that (1) the spatial distribution of elements is imaged before analysis of unknown samples and (2) it is used in conjunction with a doped glass as the primary reference material.     

Reference Minerals for the Microanalysis of Light Elements

The quantitative determination of light element concentrations in geological specimens represents a major analytical challenge as the electron probe is generally not suited to this task. With the development of new in situ analytical techniques, and in particular the increasing use of secondary ion mass spectrometry, the routine determination of Li, Be and B contents has become a realistic goal. However, a major obstacle to the development of this research field is the critical dependence of SIMS on the availability of well characterized, homogeneous reference materials that are closely matched in matrix (composition and structure) to the sample being studied. Here we report the first results from a suite of large, gem crystals which cover a broad spectrum of minerals in which light elements are major constituents. We have characterized these materials using both in situ and wet chemical techniques. The samples described here are intended for distribution to geochemical laboratories active in the study of light elements. Further work is needed before reference values for these materials can be finalized, but the availability of this suite of materials represents a major step toward the routine analysis of the light element contents of geological specimens.     

Available Clay and Feldspar Reference Samples As Standards for Archaeological Pottery Studies

The available clay and feldspar reference samples, rather than the frequently used rock reference samples, are suggested as standards for archaeological pottery studies because their trace-element contents are more like those of the artefacts. Such samples may provide a basis for correlating archaeological studies throughout the world. The assumption that bottles of such reference samples should have homogeneous trace-element contents because of the nature of the materials has been confirmed by the analysis of variance of trace -element data by instrumental neutron activation analysis.     

THE DETERMINATION OF FLUORINE BY PROTON INDUCED GAMMA RAY EMISSION SPECTROMETRY (PIGE) IN EIGHTEEN CHINESE STANDARD REFERENCE SAMPLES OF STREAM SEDIMENTS, SOILS AND ROCKS: GSD 9-12, GSS 1-8 AND GSR 1-6

Eighteen new Chinese standard reference samples (including stream sediments, soils and rocks) have been analysed by an automated proton induced gamma ray emission (PIGE) method for fluorine. Results of determinations are reported and are generally in good agreement with the "usable values" previously published.     

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

Reference Materials for Geochemical Studies: New Analytical Data by ICP-MS and Critical Discussion of Reference Values

Abundances of twenty four trace elements, including Y and fourteen rare earth elements (REE), are reported for eighty six geological reference materials and four proficiency testing samples. Analytical data were obtained by ICP-MS using solution nebulisation after mixed acid digestion (HF-HClO₄) under pressure. Analysed samples cover a wide range of element concentrations and mineralogical compositions, including samples for which there are few previously published data. Precision for elemental determinations in nearly 90% of the samples analysed is better than 5%. Accuracy, estimated by comparison with data from compilations is better than 6% for well characterized reference materials. Results obtained for samples that are low in trace elements are often significantly lower than compiled reference values. A critical discussion of the compiled data sets, especially for Y and the REEs, indicates that some reference values seem to be erroneous.     

金—银系列矿物的电子探针定量分析方法及其应用

自然界最常见的金矿物是金-银系列矿物。作者利用电子探针显微分析仪,对我国的金-银系列矿物进行研究,取得了较好的效果。本文着重介绍电子探针定量分析方法和对50个样品的研究成果。样品分别取自我国各主要产金区的不同类型金矿床。研究结果表明,金-银系列的各亚种矿物在我国均有产出,金的含量由98.18％至微量。自然银和金银矿较为少见,自然金和银金矿则是最主要的工业矿物,几乎每个金矿床的样品中都普遍存在,不同类型的样品,金矿物所含的微量元素也有差异。     

New CCRMP Reference Uranium ore BL-5 And Sulphide Concentrates CCU-I, CPB-1 and CZN-1

Under the Canadian Certified Reference Mate-vials Project (CCRMP), four new ore reference materials, one uranium ore BL-5 and three sulphide concentrates (CCV-1, CPB-1 and CZN-1) have been recently issued. The preparation, characterization and certification of these samples are briefly presented.     

DETERMINATION OF NINE RARE EARTH ELEMENTS IN EIGHT USGS REFERENCE SAMPLES AND IN THE ANRT GLAUCONITE, GL-O, BY SEQUENTIAL INDUCTIVELY COUPLED ARGON PLASMA SPECTROMETRY

Nine rare earth elements have been determined by inductively coupled plasma spectrometry (ICP) in eight USGS reference samples, MAG-1, SCo-1, SDC-1, BIR-1, DNC-1, W-2, BCR-1 and BHVO-1 and in the ANRT Glauconite, GL-O. Along with these new data, updated compilations are presented for these samples. Good agreement is observed between the present work and the compiled values.     

NEW REFERENCE SAMPLES OF MAGMATIC ROCKS: QUARTZ DIORITE SKD-1 AND SVIATONOSSITE SSV-1

The preparation and study of the two rock reference samples, Quartz Diorite SKD-1 and Sviatonossite SSv-1, are described, along with mineralogical and petrographic features. After its homogeneity studies, the two samples were analysed by seventy-five former USSR laboratories in the framework of an interlaboratory analytical program. The two samples have been certified respectively for 41 and 39 major, minor and trace elements; additionally, values are proposed for about 20 trace elements. The compiled data on the two samples are presented as an Appendix. Both the samples, processed in about 280 kg, form now part of the set of eight magmatic rock reference samples prepared by the Institute of Geochemistry in Irkutsk.     

Reproducibility Tests for INAA Determinations With AGV-I, BCR-I and GSP-I and New Data For 17 Geochemical Reference Materials

During 1975–1977, the USGS reference rocks GSP-1, BCR-1 and from 1977 onwards AGV-1 have been systematically analysed in routine INAA as test samples. The results are given for up to 26 elements per sample and the reliability of our setup is demonstrated. For further 17 geochemical reference samples, new results are presented and compared with available data.