等离子体质谱法测定天然水中痕量元素

本文利用ICP-MS分析技术检出限低,可同时测定多元素,以及溶液进样等特点,建立了天然水中多种痕量元素分析的有效方法,研究了整个测定质量范围内的背景、干扰及其克服方法,讨论了水中Na、Mg、Ca等元素产生的基体效应对被测元素的影响。对含盐量较低的天然水样,可直接测定的痕量元素达50余种,测定限为0.x—xμg/L。高盐水样如海水、卤水等的测定,本文选择共沉淀法,以Fe(OH)_3为捕集剂,使被测元素与大量的碱金属、碱土金属基体分离。分离后可测40种痕量元素,测定限为0.0x—0.xμg/L。     

A Compilation of Silicon and Thirty One Trace Elements Measured in the Natural River Water Reference Material SLRS-4 (NRC-CNRC)

The natural river water certified reference material SLRS-4 (NRC-CNRC, National Research Council-Conseil National de Recherches Canada) has been routinely analysed for major and trace elements by six French laboratories. Most measurements were made using inductively coupled plasma-mass spectrometry. For silicon and thirty one trace elements (rare earth elements, Ag, B, Br, Cs, Ga, Ge, Li, P, Pd, Rb, Se, Th, Ti, Tl, W, Y and Zr), no certified values are assigned by NRC-CNRC. We propose some compilation values and related uncertainties according to the results obtained by the different laboratories.     

Determination of Trace Elements in Twenty Six Chinese Geochemistry Reference Materials by Inductively Coupled Plasma-Mass Spectrometry

We report new data for thirty seven elements determined in twenty six Chinese geochemistry reference materials using inductively coupled plasma-mass spectrometry and a reliable and simple dissolution technique. One hundred milligrams of sample were digested with 1 ml of HF and 0.5 ml of HNO₃ in PTFE-lined stainless steel bombs heated to 200 °C for 12 hours. Insoluble residues were dissolved using 6 ml of 40% v/v HNO₃ heated to 140 C for 3 hours. Analytical calibration was accomplished using aqueous standard solutions. Rhodium was used as an internal standard to correct for matrix effects and instrument drift. Precisions were typically better than 5% RSD. Most of the data presented here agree well with the published certified values. For the elements Zr, Hf and most other trace elements, the measured values were less than 10% in error when compared to certified values.     

黑色页岩样品中痕量级铂族元素地球化学成分标准物质研制

介绍了黑色页岩样品中6个铂族元素铂、钯、钌、锇、铑、铱的标准物质研制过程。黑色页岩样品采自贵州黄家湾,为一次采集、一次混样的原始样品,随机抽取包装好后的样品进行检验与定值。均匀性、稳定性符合要求后,按照国际标准化组织(ISO)34、35指南的基本要求和我国一级标准物质的技术规范,采用多个实验室协同测试的定值方式,利用不同原理的分析方法对此样品的6个铂族元素进行定值。以各实验室组数据作为最小统计单元,用Grubbs准则、Dixon法检验剔除离群数据,Shapiro-Wilk法检验各元素数据分布的正态性。检验结果100%的元素呈正态或近似正态分布。定值的6个元素均符合标准值水平。     

Determination of Rare Earth Elements in Geological Reference Materials: A Comparative Study by INAA and ICP-MS

Data was obtained for the rare earth elements (REE) by instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) in twenty geological reference materials. In general, the precision obtained by ICP-MS is better for the light REE, decreasing with increasing atomic number. This is partly a result of the occurrence of the heavy REE at low concentrations. The precision of the data obtained by INAA is good (5% RSD). The data obtained also showed that for the elements determined by both methods, the accuracy is similar for the light REE and better for the middle and heavy REEs by INAA. Higher uncertainty is achieved by ICP-MS mainly for elements at very low concentrations, occurring at about ten times the chondritic values.     

Determination of Bromine and Iodine in Twenty-three Geochemical Reference Materials by ICP-MS

Trace amounts (from nanogram to microgram levels) of bromine and iodine were determined by inductively coupled plasma-mass spectrometry (ICP-MS) in twenty-three geochemical reference materials issued by the GSJ, USGS, IAEA etc. The pyrohydrolysis technique was used to separate bromine and iodine from samples analysed in the form of powder. The accuracy and precision of the experimental values were assessed by the comparative analysis of well established reference materials such as USGS AGV-1, BCR-1 and IGGE GBW07312. The measured values agreed well with reported values within a 10% error range. We also report reliable new data for these elements in these geochemical reference materials.     

电感耦合等离子体质谱直接测定冰芯样品中痕量铅

利用电感耦合等离子体质谱仪对冰芯样品中超痕量Pb进行了直接测定。确定了测定溶液中浓度为ng/L级Pb的最佳仪器参数，载气流速、进样速度等与灵敏度之间的关系,浓度和扫描参数对分析精度的影响。仪器对Pb的质量浓度在20～100ng/L的分析精度(RSD，n=3)＜10%,标准加入回收率在85%～115%，检测下限为0.62ng/L，并给出了采自可可西里马兰冰川M3冰芯中Pb的分析结果。     

地质标准物质中痕量元素量值溯源性探讨

标准物质的特性量值应该具备溯源性。然而地质标准物质溯源性的建立往往是很困难的。对痕量元素量值溯源的若干难点进行了讨论;提出了建立标准物质研制的质量体系的建议并就相关问题进行了阐述;应重视量值的信息反馈,提高定值的质量。     

铂族元素地球化学标准物质的研制

ＧＰｔ＿１～７系列标准物质由土壤、水系沉积物、富镁超基性岩、富铁超基性岩、含铜镍贫铂矿石及铬铁矿等不同类型７个样品组成。铂族元素的含量范围从土壤和岩石的背景含量到矿石达４～５个数量级。经方差检验样品均匀度良好。标准物质的定值分析采用了不同类型的试金和湿化学法分离富集,以原子吸收、催化比色、催化极谱、等离子体质谱、发射光谱和中子活化等方法进行测定。定值的元素为Ｐｔ、Ｐｄ、Ｏｓ、Ｒｕ、Ｉｒ、Ｒｈ６个铂族元素及Ａｕ。该系列标准物质主要适于作铂族元素地球化学勘查和铂矿勘查中铂族元素分析的量值标准与测试的质量监控。     

New REE and Trace Element Data on Two Kimberlitic Reference Materials by ICP-MS

Data on thirty-four minor and trace elements including all rare earth elements (REE) are reported for two kimberlitic international reference materials (SARM-39, MINTEK, RSA and MY-4, IGEM, Russia) by inductively coupled plasma-mass spectrometry (ICP-MS), some of them for the first time. Four digestion techniques (open acid, closed vessel acid, microwave and lithium metaborate fusion digestion) were used for the decomposition of samples for analysis by ICP-MS. Three other reference materials (USGS BHVO-1, CRPG BR-1 and ANRT UB-N) were analysed simultaneously using the same analytical methodology to assess the precision and accuracy of the determinations. The data obtained in this study compare well with working values wherever such values are available for comparison. Though open acid digestion was found to be very rapid, effective and convenient for the determination of several trace elements in kimberlitic samples, recoveries for heavy rare earth elements (HREE) were lower than the respective recoveries obtained by the other decomposition techniques used. The precision obtained was better than ± 6% RSD in the majority of cases with comparable accuracy. Chondrite-normalised plots of each RM for all the digestion techniques were smooth. The new data reported on the two kimberlitic reference materials make these samples useful for future geochemical studies of kimberlitic rocks.     

Synthetic Silica Glass for Trace Aluminium Determination in Quartz by Electron Microprobe

Five synthetic silica glasses have been prepared for microprobe determination of trace aluminium in quartz. The glasses were synthesized from tetraethoxysilane (TEOS) into which between 0 and 1431 μg g-¹ aluminium had been doped. The aluminium concentrations of the glasses were independently determined by ICP-AES analysis. X-ray wavelength shift in the Al Kα peak was minimised relative to unknown quartz samples when these glasses were used for calibration. A set of these five glasses yielded a linear calibration line, and are available for trace aluminium analysis of quartz in routine microprobe systems.     

Boron Determination in Twenty One Silicate Rock Reference Materials by Isotope Dilution ICP-MS

The concentration of boron was determined in twenty one geochemical reference materials (silicate rocks) by isotope dilution inductively coupled plasma-mass spectrometry. Boron was extracted from the rocks using HF digestion, suppressing boron volatilisation through boron-mannitol complexation. Sample solutions, in a diluted HCl matrix, were analysed by ICP-MS without any separation of boron from the matrix elements. The results obtained were in agreement with the literature data and indicate that using the described procedure, trace amounts of boron can be very easily determined in complex matrices with rapidity and precision. With the instrumentation and reagents used in this study, this procedure can be used for the determination of 0.5 μg g⁻¹ boron in a 15 0 mg silicate rock sample. Replicate analyses of the twenty one geochemical reference materials (GRM), ranging in boron concentration from 1.35 to 15 7 μg g⁻¹, yielded precisions (relative standard deviation) varying between 0.9 and 9.8%.     

金矿石化学物相分析标准物质的研制

介绍了金矿石化学物相分析标准物质的研制工艺及技术关键，列出了单体金、连生体金、硫化物包裹金、其他矿物包裹金及总金的原始数据和定值数据。经9个实验室共同分析协作，研制的5个标准物质已被国家质量监督检验检疫总局批准为国家一级标准物质。该系列标准物质主要用于金矿石化学物相分析质量监控、分析方法评价等。     

Four Natural Chromite Reference Materials for the Determination of the First-Row Transition Elements and Gallium by LA-ICP-MS

Four natural chromite samples (LBS13-04, LBS13-06 and LBS13-13) from the Luobusa ophiolite (China) and 16SW2-6 from the Stillwater Complex (USA) were developed as reference materials for in situ element microanalysis. Approximately 8 g of chromite fragments with grain sizes of 0.5–1.5 mm from each chromite sample were separated under a binocular microscope and analysed by EPMA, XRF, LA-ICP-MS and solution nebulisation ICP-MS techniques for major and trace elements at six laboratories. The results show that the four chromite samples are homogeneous with respect to MgO, Al₂O₃, Cr₂O₃, FeO, Sc, Ti, V, Mn, Co, Ni, Zn and Ga. These samples are thus suitable to be used as reference materials for in situ microanalysis.     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

Fitness-for-Purpose of Reference Material Reference Values in Relation to Traceability of Measurement, as Illustrated by USGS BCR-1, NIST SRM 610 and IAEA NBS28

As in all fields of sample analysis, reference materials play a large role in supporting measurements in the geosciences. While a rather large number of materials are in distribution (> 380), not all are equally effective or fit-for-purpose in supporting laboratory data quality and thereby assuring the desired comparability of measurements between laboratories. Equally important, reference values that are not fit-for-purpose cannot be used effectively to establish traceability links between laboratory measurements and national and international standards. The needed fitness-for-purpose is not achieved for reference values either when more than one reference value has been proposed and a consensus does not exist among users as to which should be used by all, or when reference value uncertainties are too large in comparison to those of routine laboratory measurements. The focus of this review will be, first to outline the current reality, and second to suggest ways in which certifications of RMs can be improved to provide reference values that are universally accepted and more fit-for-purpose in general laboratory use. The discussion will be illustrated largely by current uses of USGS BCR-1, NIST SRM 610 and IAEA NBS28, as these three materials are those for which the largest body of newly published data exists, according to recent bibliographies of the geoanalytical literature published annually in Geostandards Newsletter: The Journal of Geostandards and Geoanalysis.     

Determination of Trace Elements in BCS CRM 313/1 (BAS) and NIST SRM 1830 by Inductively Coupled Plasma-Mass Spectrometry and Instrumental Neutron Activation Analysis

In the past, there has been little interest in the trace element characteristics of quartz, and in consequence little activity in the trace element characteristics of reference materials with high silicon content. The main purpose of this paper is to contribute to the characterisation of two international certified reference materials, BCS 313/1 from the Bureau of Analysed Samples, (BAS), UK and SRM 1830 from the National Institute of Standards and Technology (NIST), USA. BCS 313/1 was analysed by laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), solution ICP-MS and instrumental neutron activation analysis (INAA). NIST SRM 1830 was analysed by LA-ICP-MS and INAA. Analytical results are reported for more than forty elements, most of them for the first time. For most elements, the results obtained by the different methods agree within 15 % relative. The recent, heightened interest in quartz and in particular the precise determination of trace0element contents in natural quartz samples requires the use of well characterised reference materials such as BCS 313/1 and SRM 1830, to which this study is designed to contribute.     

大管回流消解ICP-MS测定植物样品中的Hg及其他痕量元素

针对易挥发元素Hg提出了大试管和红外加热的多孔控温消解炉的简单装置消解植物样品的大管回流法。该方法结合ICP-MS测定Hg,指出在0.18%L-半胱氨酸加入内标做清洗液消除汞的记忆效应,校准曲线有一个更好的相关系数r=0.9993,Hg的测定限可达0.012μg/g(10σ,DF=100);并比较了原子荧光测定Hg的测定限0.0013μg/g(10σ,DF=100)和测定结果。该方法经标准物质GSV-3、GSV-4、GSB-1、GSB-6、GSB-10和GSB-4验证,测定值与标准值基本吻合。实验结果表明,该消解方法中Hg基本没有损失,而且ICP-MS的测定Hg的同时可以测定Li、B、Cr、Mn、Co、Ni、Cu、Zn、As、Sr、Mo、Cd、Ba和Pb等痕量元素。     

感耦等离子体质谱法同时测定岩石中痕量元素的研究

试验了含难熔组分的岩石样品的分解方法、熔剂用量，以及溶液中可溶盐量的控制和标准系列的熔剂匹配等问题；分别采用Ｒｅ、Ｒｈ和Ｉｎ作内标，解决了基体效应及其基体导致的灵敏度漂移的影响，实现了不经分离富集直接用ＩＣＰ－ＭＳ法测定岩石样品中３４个痕量元素。方法测定限０．０１～５μｇ／ｇ，ＲＳＤ（ｎ＝１０）为２．６％～１３％，已应用于地质试样分析，岩石标样分析结果与标准值相符。