An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

Production and Certification of Synthetic Selenium Isotopic Reference Materials

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.     

Automated Extraction of a Five‐Year LA‐ICP‐MS Trace Element Data Set of Ten Common Glass and Carbonate Reference Materials: Long‐Term Data Quality,Optimisation and Laser Cell Homogeneity

LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.     

Effect of the Dry Ashing Method on Cadmium Isotope Measurements in Soil and Plant Samples

A dry ashing method is commonly used to remove organic material from samples prior to geochemical analysis. In the course of this study, the Cd isotope ratios of a series of soil and plant reference materials and samples were studied to evaluate the effect of the dry ashing method on measurement results of Cd isotope ratios. The samples were pre‐treated using the dry ashing method and high‐pressure bomb for comparison. The results show that the digestion using high‐pressure bombs did not lead to Cd loss, but using the dry ashing method would cause different proportions of Cd loss. The whole range of Cd isotope difference between two methods was from ?0.07‰ to 3.01‰. There was also an obvious difference in measured Cd isotope ratios from the same leaf sample pre‐treated independently by the dry ashing method, indicating that the amount of Cd loss and the effect on Cd isotope measurement during dry ashing is related to the properties of the samples. Therefore, dry ashing may not be appropriate for the removal of organic material in Cd isotope ratio measurement, especially for samples with high organic contents. The δ^114/110Cd values of reference materials NIST SRM 1573a and GSD‐30 are reported for the first time in this study.     

一种由粗到精的地面激光点云多层级配准方法

提出了一种综合利用快速点特征直方图(FPFH)描述符和同名点引导ICP优化的地面激光扫描(TLS)点云配准方法。该方法包括3个步骤:1)点云金字塔构建;2)基于FPFH的粗配准;3)同名点引导的ICP精配准。首先使用体素网格滤波器构造点云的金字塔结构,在粗配准时,FPFH描述符用于金字塔顶层上点云的鲁棒匹配,在此基础上,再进行两层级同名点引导的ICP精配准优化,使用3组典型TLS点云对进行实验,结果表明本文方法可以高效地完成TLS点云的配准。     

Effect of different registration methods on precision of orientation based on RTK registration/georeferencing mode

Abstract

Compared with traditional methods, the three-dimensional laser-scanning (3D-LS) technique can efficiently acquire many high-quality geometric properties of rock discontinuities. In practice, engineers usually prefer to simplify the processing by using single-station point data and roughly orienting owing to the complexity of registration/georeferencing multi-station point data. However, prior published studies have paid little attention to the accuracy and reliability when determining discontinuity orientations using 3D-LS. We propose a reliable and accurate method with robust on-site applicability. As part of an ongoing effort, we are evaluating the precision of the commonly used coarse registration method and the fine registration method, and promoted the optimized coarse- and fine-registration methods and evaluated their precision. It is found that: (1) the common and the optimized registration method can meet our project’s engineering requirements, and the optimized registration method improved accuracy in the dip direction by approximately 1°; (2) fine registration using an iterative closest point (ICP) algorithm can correct both dip direction and dip angle; and (3) the orientation is of high precision with commonly used coarse and fine registration, whereas the optimization effect to correct the orientation is slightly limited.     

不同测站点云数据的配准算法

随着三维激光扫描技术的发展,利用三维激光扫描仪采集信息,构建三维模型成为了热门的课题。由于受到观测环境、观测方向等影响,无法一次性地获得物体的所有的点云数据。因此,不同视角下点云数据的配准成为了三维建模中的关键技术,直接影响了最终的重合结果以及模型精度。本文着重研究主方向贴合法和最近点迭代算法(ICP算法),基于matlab平台编写算法,并对算法进行研究,得出配准结果以及配准精度。     

海洋沉积物中多种元素的ICP光谱分析

报道了用王水-HF溶样,ICP-AES同时测定海洋沉积物中18种常量、微量元素的方法.该方法简便、快捷,其准确度、精密度及检出限均好.     

陡倾斜脉状矿体隐伏深度计算

在研究广西 10 0个矿区地质资料基础上 ,建立了陡倾斜脉状矿体隐伏深度计算经验公式 ,从而为隐伏矿床预测、减少矿床勘查风险提供了信息     

地幔流体及其成矿作用

高灵敏度、高精密度、低检出限、多元素同时检测并可提供同位素组成比值信息的等离子体质谱与高空间分辨率的紫外激光采样技术结合 ,可定量地测定单个流体包裹体中常、微量元素含量 ,为成矿流体的研究提供了一个新的研究手段。文中简要地介绍了激光剥蚀电感耦合等离子体质谱 (LA ICP MS)分析仪器的发展 ,结合实验室的研究工作 ,就激光剥蚀池的设计、单个流体包裹体的剥蚀方法、元素的分馏效率、定量校正技术及其在成矿成因物理化学机制研究中的应用等进行评述 ,并阐述单个流体包裹体元素组成的LA ICP MS分析技术存在的局限和发展趋势。