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1.
In this paper, we provide a detailed account of our sample fusion, calibration and instrumentation methods for major-element whole-rock analysis by XRF, and we discuss several aspects of sample preparation and instrument performance that are important considerations for accurate analysis. The fusion procedure involves moderate capital costs and is easy to apply, yielding flat, polished, homogeneous glass discs as cast. The calibration method utilizes a least-squares procedure that rigorously fits data according to both compositional and counting statistical uncertainties. We use a side-window Rh tube for analyzing major elements (including Na) and employ real-time testing for constant count rate to reject spurious results.

The methods result in excellent analytical precision and reproducibility. The standards used for calibration lie within compositional and counting statistical uncertainties of best-fit straight lines. Analyses of replicate discs and repeated analyses of single discs show excellent long-term reproducibility over several months, approaching counting statistical uncertainties in several cases. Comparison with independent measurements made by other laboratories using instrumental neutron activation and X-ray fluorescence analyses shows excellent agreement with our results.

A side-window Rh tube gives increased detection limits for most major elements, but otherwise shows little difference in precision compared to a Cr tube. This means that major and trace elements can be analyzed without changing X-ray sources, which provides saving in terms of time and money, as well as being a convenience to the analyst.  相似文献   


2.
A simple flux‐free fusion technique was developed to analyse major and trace element compositions of silicate rocks. The sample powders were melted in a molybdenum capsule sealed in a graphite tube to make a homogenous glass in a temperature‐controlled one‐atmosphere furnace. The glass was then measured for both major and trace element concentrations by LA‐ICP‐MS using a calibration strategy of total metal‐oxide normalisation. The optimum conditions (i.e., temperature and duration) to make homogeneous glasses were obtained by performing melting experiments using a series of USGS reference materials including BCR‐2, BIR‐1, BHVO‐2, AGV‐1, AGV‐2, RGM‐1, W‐2 and GSP‐2 with SiO2 contents from 47 to 73% m/m. Analytical results of the USGS reference materials using our method were generally consistent with the recommended values within a discrepancy of 5–10% for most elements. The routine precision of our method was generally better than 5–10% RSD. Compared with previous methods of LA‐ICP‐MS whole‐rock analyses, our flux‐free fusion method is convenient and efficient in making silicate powder into homogeneous glass. Furthermore, it limits contamination and loss of volatile elements during heating. Therefore, our new method has great potential to provide reliable and rapid determinations of major and trace element compositions for silicate rocks.  相似文献   

3.
Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) is a high spatial resolution analytical method which has been applied to the analysis of silicic tephras. With current instrumentation, around 30 trace elements can be determined from single glass shards as small as ～ 40 µm, separated from tephra deposits. As a result of element fractionation during the ablation process using a 266 nm laser, a relatively complex calibration strategy is required. Nonetheless, such a strategy gives analyses which are accurate (typically within ±5%) and have an analytical precision which varies from ～ ±2% at 100 ppm, to ～ ±15% at 1 ppm. Detection limits for elements used in correlation and discrimination studies are well below 1 ppm. Examples of the application of trace element analysis by LA‐ICP‐MS in tephra studies are presented from the USA, New Zealand and the Mediterranean. Improvements in instrumental sensitivity in recent years have the potential to lower detection limits and improve analytical precision, thus allowing the analysis of smaller glass shards from more distal tephras. Laser systems operating at shorter wavelengths (e.g. 193 nm) are now more widely available, and produce a much more controllable ablation in glasses than 266 nm lasers. Crater sizes of <10 µm are easily achieved, and at 193 nm many of the elemental fractionation issues which mar longer wavelengths are overcome. By coupling a short wavelength laser to a modern ICP‐MS it should be possible to determine the trace element composition of glass shards as small as 20 µm and, providing sample preparation issues can be overcome, the determination of the more abundant trace elements in glass shards as small as 10 µm is within instrumental capabilities. This will make it possible to chemically fingerprint tephra deposits which are far from their sources, and will greatly extend the range over which geochemical correlation of tephras can be undertaken. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

4.
To test whether the silicate reference glasses BAM‐S005‐A and BAM‐S005‐B from BAM (The Federal Institute for Materials Research and Testing, Germany) are suitable materials for microanalysis, we investigated the homogeneity of these reference glasses using the microanalytical techniques EPMA, LA‐ICP‐MS and SIMS. Our study indicated that all major and most trace elements are homogeneously distributed at micrometre sampling scale in both types of glass. However, some trace elements (e.g., Cs, Cl, Cr, Mo and Ni) seem to be inhomogeneously distributed. We also determined the composition of BAM‐S005‐A and BAM‐S005‐B. The EPMA data of major elements confirmed the information values specified by the certificate. With the exception of Sr, Ba, Ce and Pb, our trace element data by LA‐ICP‐MS were also in agreement with the certified values within the stated uncertainty limits. The reasons for the discrepancy in these four elements are still unclear. In addition, we report new data for twenty‐two further trace elements, for which the concentrations were not certified. Based on our investigation, we suggest that both of these materials are suitable for many microanalytical applications.  相似文献   

5.
A simple, rapid and precise method is described for determining trace elements by laser ablation (LA)-ICP-MS analysis in bulk geological materials that have been prepared as lithium borate glasses following standard procedures for XRF analysis. This approach reliably achieves complete sample digestion and provides for complementary XRF and LA-ICP-MS analysis of a full suite of major and trace elements from a single sample preparation. Highly precise analysis is enabled by rastering an ArF excimer laser (λ= 193nm) across fused samples to deliver a constant sample yield to the mass spectrometer without inter-element fractionation effects during each analysis. Capabilities of the method are demonstrated by determination of twenty five trace elements (Sc, Ti, V, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf, Ta, Pb, Th and U) in a diverse range of geological reference materials that includes peridotites, basalts, granites, metamorphic rocks and sediments. More than 90% of determinations are indistinguishable from published reference values at the 95% confidence level. Systematic bias greater than 5% is observed for only a handful of elements (Zr, Nb and U) and may be attributed in part to inaccurate calibration values used for the NIST SRM 612 glass in the case of Zr and Nb. Detection limits for several elements, most notably La, are compromised at ultra-trace levels by impurities in the lithium borate flux but can be corrected for by subtracting appropriate procedural blanks. Reliable Pb analysis has proved problematic due to variable degrees of contamination introduced during sample polishing prior to analysis and from Pt-crucibles previously used to fuse Pb-rich samples. Scope exists for extending the method to include internal standard element/isotope spiking, particularly where integrated XRF analysis is not available to characterise major and trace elements in the fused lithium borate glasses prior to LA-ICP-MS analysis.  相似文献   

6.
In this study, we used the modified Horwitz expression (Hc= 0.01c0.8495, which gives the precision as a function of concentration) to evaluate and control the accuracy of results of silicate rock analysis obtained by X-ray fluorescence spectrometry. This expression is currently used by the organisers of the GeoPT international proficiency tests, to assign the precision limits of each analyte and subsequently to evaluate the data provided by laboratories whose main application is geochemistry. Results for major and trace elements, determined in glass disk and pressed pellets, respectively, were evaluated. Nine international silicate rock reference materials were analysed and results were compared to the recommended values plus and minus the limits given by the above expression. Those limits are easily attained for most major elements, but not for trace elements. Sample preparation and sub-sampling contributions to precision were evaluated by analysis of an in-house reference sample. In our results, precision does not follow the Horwitz expression relationship with concentration. It is known that the final accuracy in XRF analysis depends strongly on instrumental settings and on the uncertainties associated with the certified or recommended values of the reference materials used to calibrate the spectrometer, but our results indicate that the precision expression can be useful, especially to inspect and correct calibration curves and to check routine instrumental accuracy.  相似文献   

7.
探索了利用高温炉合成玄武岩玻璃制作原位微区主微量元素含量分析的标准物质的实验条件.选取玄武岩标准物质GBW07105(GSR-3)进行高温熔融、淬火实验研究,获得玄武岩玻璃,为合成其他地质样品微区分析标准参考物质的研制提供了参考方法.用激光剥蚀-四极杆等离子体质谱(LA-Q-ICPMS)对样品微区46个主元素和微量元素...  相似文献   

8.
玻璃固化是一种常用的高放废液固化方法,其优点在于具有较高的抗化学介质侵蚀的能力和很好的辐照稳定性、热稳定性和机械稳定性,其不足之处在于抗水浸出等性能有所下降而使其安全性需要进一步通过抗浸出实验来进行衡量和确认。使用二次离子质谱(SIMS)分析玻璃固化体中的放射性成分(如铀元素)的分布及浸出行为等各项指标,是一种评估玻璃固化体抗浸出性能的分析手段。本文应用SIMS测试模拟玻璃固化体,以碳作为镀膜材料通过真空蒸发镀碳的方法优化样品制备条件,有效地解决了样品导电性差的问题,~(235)U/~(238)U同位素测定结果约为7.9‰±0.395‰,基本符合制作模拟样品时所使用的天然铀的同位素特征(~(235)U/~(238)U参考值约7.3‰)。研究表明,建立的方法实现了铀元素同位素丰度的测量,能直接显示铀的分布情况,该方法可为研究玻璃固化体中放射性元素的浸出行为提供一定的技术支持。  相似文献   

9.
For the trace element analysis of gold by laser ablation ICP-MS, external calibration samples of differing matrix composition have been used in previous studies. Data presented here suggest that even for calibration samples and unknowns with closely-matched matrices, discrepancies arise due to variations in the coupling behaviour of the laser with the sample at different power deliveries, and can lead to erroneous trace element determinations. Internal standardisation for gold is complicated because Au and Ag, the most common major elements, do not have minor isotopes that can be used as internal standards. This problem was overcome for natural gold samples by using an external calibration sample only for the major elements Au and Ag, then defocussing the ion path and using 107Ag in each sample as an internal standard against which μg g-1 levels of Te, Sb, Hg, Bi, and Cu were determined. The results suggest that trace elements can occupy lattice sites in gold rather than occurring only as micro-inclusions of other phases. The analytical approach taken here may be used in trace element analysis where adequate external calibration samples are not readily available.  相似文献   

10.
It is possible that placer gold retains the trace element composition (`signature') of the parent lode. Laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) offers sensitive detection limits of 59 elements with sub-millimetre sample spot sizes, ideal for signature analysis of placer. Here, the optimum laser parameters, analytical precision and reproducibility of elemental signatures are determined in placer nuggets by infrared LA–ICP–MS. The highest precision was offered by Q-switched ablation at a relatively low energy level, using Au as an internal standard; these parameters gave median precision values of 33–82% RSD for trace elements in nuggets. In addition to major constituents such as Ag, Cu and Hg, placer from several rivers world-wide commonly contained a wide range of trace elements including, in some cases, unusual REE patterns. At least two distinct signatures could be distinguished in placer from most of the rivers examined, while multiple examples of certain signatures were also seen. Tracking these signatures back to their original tributaries may offer a means of identifying the number and approximate location of deposits within a river watershed, thereby significantly aiding exploration.  相似文献   

11.
Results are presented for round one of a new international proficiency testing programme designed for microprobe laboratories involved in the routine analysis of silicate minerals. The sample used for this round was TB-1, a basaltic glass fused and prepared by the USGS. Thirty nine laboratories contributed data to this round, the majority of major element results being undertaken by EPMA and the majority of trace elements by LA-ICP-MS. Assigned values were derived from the median of results produced by nine selected laboratories that analysed powdered material by conventional ICP-MS, INAA and XRF techniques using bulk powders of the sample. Submitted microprobe results were evaluated using a target precision calculated using the Horwitz function, adopting the same criteria as those used for "applied" geochemistry laboratories in the companion GeoPT proficiency testing programme for laboratories involved in the routine bulk analysis of silicate rocks. An evaluation of results from participating microprobe laboratories indicated that overall, data were compatible with this precision function. A comparison between the performance of bulk and microprobe techniques used in the analysis of the basaltic glass showed remarkably good agreement, with significant bias only observed for the major oxide MgO.  相似文献   

12.
In this contribution we evaluate the capabilities of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) using a 12 μm spot size. Precision, accuracy and detection limits were assessed on the USGS BCR-2G reference material. We demonstrate that the 12 μm LA-ICP-MS analyses of experimentally-grown amphibole and garnet are in excellent agreement with secondary ion mass spectrometry (SIMS) trace element determinations on the same crystals. The 12 μm spot size configuration was subsequently used to determine trace element crystal-melt partition coefficients (Dc/m) for a wide range of trace elements in amphibole in equilibrium with a basanitic melt. The following strategy to determine accurately and evaluate Dc/m is proposed. One or more major elements determined previously by electron probe microanalysis (EPMA) was used to ensure consistency between EPMA and the composition of the aerosol produced by the laser ablation. Measured Dc/m values were successively evaluated using the lattice strain model. The use of this strategy significantly improved the precision and accuracy of Dc/m determination when a LA-ICP-MS configuration with a high spatial resolution was employed.  相似文献   

13.
氢化物发生-原子荧光光谱法同时测定滑石中砷和汞   总被引：3，自引：2，他引：1  
样品经盐酸、硝酸、氢氟酸、高氯酸溶解,盐酸提取,提取液直接上机测定。综合采用离峰背景校正法及干扰系数校正法消除各种干扰对测定的影响,电感耦合等离子体发射光谱法测定煤及煤灰样品中21个主次量及微量元素。方法检出限为0.03~5.6μg/g,精密度(RSD,n=11)为0.5%~3.6%。方法用国家一级标准物质验证,各元素的测定值与标准值吻合,满足煤分析要求。  相似文献   

14.
Fifty elements in NIST SRM 614 and 616 glass reference materials were determined by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). The values determined for NIST SRM 614 agreed well with the NIST-certified and information values (mean relative difference ± 3.6%), except for B, Sc and Sb. The values determined for NIST SRM 616 agreed with the NIST-certified and information values within a mean relative difference of ± 1.5%, except for B, Sc and Ga. In addition, at an 80 μm sampling scale, NIST SRM 614 and 616 glass discs were homogeneous for trace elements within the observed precisions of 5 and 15% (mean), respectively. Detection limits were in the range 0.01 - 0.3 μg g−1 for elements of lower mass numbers (amu < 80) and 1 - 10 ng g−1 for heavy elements (amu > 80). Detection at the sub ng g−1 level is possible for most of the heavy elements by using an ablation pit size larger than 10 0 μm.  相似文献   

15.
The paper presents preliminary results of the use of a high resolution double-focussing, magnetic sector inductively coupled plasma-mass spectrometer (HR-ICP-MS) with ultraviolet laser ablation (LA) for the bulk analysis of geological materials fused with Li2B4O7. Detection limits are based on data from precision measurements of a fused SiO2 sample of high purity, and sensitivity data (cps/μg g-1) obtained on the Reference Material (RM) Syenite SY-2. For many trace elements, the detection limits are better than 0.05 μg g-1 using a sample to flux weight ratio of 1:7.
Calibration curves, which are based entirely on RMs, are established for Hf, Ta, Tb, Tm and Lu. They indicate that, even at this early stage in the development of the technique, data accurate to ˜ 25% can be collected. It is concluded that the method may prove to be a valuable supplement to XRF for low level element concentration measurements; it is also very practical, as the same sample discs can be used for both XRF and LA-ICP-MS analyses.  相似文献   

16.
Major and trace element compositions of fifteen silicate rock reference materials have been determined by a combined XRF and laser ablation ICP‐MS (LA‐ICP‐MS) technique on glasses prepared by fusing the sample with a lithium borate flux (sample:flux = 1:3). Advantages of this technique include the ability to measure major and trace element abundances on a single sample using a quick and simple preparation that attacks resistant phases such as zircon without the need for acid dissolution. The method is suitable for a wide variety of bulk compositions including mafic, intermediate and silicic rocks. Abundance‐normalized mass response patterns (the ratio of signal intensity to element concentration) of the LA‐ICP‐MS analyses vary systematically with major element composition, demonstrating the presence of a matrix effect that cannot be compensated by normalisation to a single internal standard element. Increasing the sampling distance between the ICP‐MS cone and the torch reduces the magnitude of this effect, suggesting that a mechanism related to residence time of ablated particles in the plasma may be at least partially responsible for the observed variations in mass response patterns. When using a matrix‐matched calibration, agreement of the LA‐ICP‐MS results with published reference values or those obtained by solution ICP‐MS is 10% relative. Analytical precision based on replicate analyses is typically 5% RSD. Procedural detection limits that include contributions from gas background and flux are 0.01‐0.1 μg g‐1 for the heavy mass trace elements (Rb‐U). Major element analyses by XRF show excellent agreement with results obtained using a conventional heavy element absorbing flux. High quality major and trace element data for silicate rocks can be achieved by a combined XRF and LA‐ICP‐MS analysis of Li2B4O7/LiBO2 fused glasses provided an appropriate matrix‐matched calibration is adopted.  相似文献   

17.
A procedure for the digestion and analysis of quartz samples was developed to measure trace element concentrations in natural quartz. The certified glass sand reference material UNS-SpS was chosen to assess the precision, accuracy and detection limit of the analytical method. Quartz was digested with HF/HNO3 in a closed glassy carbon vessel and analysed by means of quadrupole ICP-MS with external calibration. Analyte concentrations of the sand UNS-SpS were compared with certified and other values from the literature. The abundances of a number of elements (Pr, Gd, Ho and Er) in the reference material are reported here for the first time. The procedure was then applied to three quartz samples from different geological settings to show that trace element data by ICP-MS can distinguish the origin of the sample.  相似文献   

18.
高岭土作为重要的铝硅酸盐,其微量元素的含量决定着高岭土产品的性能指标.高岭土的三种国家标准物质成分GBW03121、GBW03122、GBW03122a中均未含有As、Sb等10种微量元素的标准值,在高岭土的检测中只能采用近似的岩石标准物质作为监控物质,对高岭土组分的准确分析有一定影响.本文通过微波消解技术,对比了硝酸...  相似文献   

19.
全岩样品主元素和微量元素的准确测试是地球科学研究的重要手段和依据.传统溶液进样ICP-MS元素测试方法制样和测试所需周期较长(两周以上).相对溶液进样法而言,激光剥蚀系统与ICP-MS联用测试全岩粉末熔融玻璃的方法可以大大地提高测试效率.在前人研究基础上,针对前人熔融制样中Pb、Zn元素的严重丢失问题,研究了Pb、Zn...  相似文献   

20.
This paper describes a technique for the preparation of a titanite (CaTiSiO5) glass calibration material for use in in situ microanalysis of major, minor, and trace elements in geological materials. The starting composition was a titanite matrix doped with minor and trace elements at ∼ 200 μg g-1. The elements Sc, Y, REEs, Th and U were added in the form of nitrates in solution, and the elements V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Hf and W were added as solid oxides. The synthetic titanite glass was produced by direct fusion by resistance heating in graphite electrodes at 1600-1700 °C, and quenched in air. Backscattered electron images indicate good homogeneity, with no signs of separate phases or vesicles, and analysis of the major elements Ca, Ti and Si by electron microprobe showed relative standard deviations between 0.5 and 0.7%, based on six independent measurements. Deviations from nominal concentrations for Ca, Si and Ti were measured to -1.2, -3.3 and -0.8%, respectively. The homogeneity of the trace elements in the glass was assessed by LA-ICP-MS analyses, using NIST SRM 610, 612 and 616 as external calibrators, and Ca as the internal standard element. Determinations were made both with a quadrupole mass spectrometer and a sector field instrument, and both raster and spot modes of analysis were used. For the majority of doped elements, precision was better than 10%, and relative deviations from nominal values were, with few exceptions, between 5 and 10%.  相似文献   

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