地球化学标准物质的研制与应用

1978年以来,物化探研究所围绕我国地球化学调查和地质矿产勘查的需要,先后研制了多种地质物料的系列地球化学标准物质,包括水系沉积物、土壤(含全量和生物有效成份)、岩石、生物、光谱分析标准、多金属矿石与精矿、痕量铂族元素与铂矿石、痕量金与金矿石及银矿石标准物质,共计126个样品。具有系列性好和适用性强的特点,是我国地质测试质量体系的基本组成部分,其中GSD、GSS和GAu系列作为全国区域地球化学样品分析的量值和质量监控标准,保证了各省区不同时间、不同实验室的分析结果可以统一对比和成图。这些标准物质在我国地质矿产、冶金、农业、环境部门和科研院校中广泛应用,应用的国家达30余个。     

Platinum-Group Element Geochemical Certified Reference Materials (GPt1-7)

Unlike the situation for other elements, few reference materials certified for the platinum-group elements are currently available. Therefore, the GPt1-7 series of PGE geochemical CRMs, prepared by the IGGE, represent an important addition and comprise a range of matrix types, including a soil, stream sediment, Mg-rich ultramafic rock, Fe-rich ultramafic rock, platinoid ore depleted in Cu, Ni and Fe, and a chromitite. The concentration of PGE in these samples ranges over 4-5 orders of magnitude and the samples were shown to have good homogeneity as assessed by a variance test. Analytical methods based on different principles were used in sample certification, including several fire assay and wet chemical procedures used for decomposition and preconcentration. Certified values for the elements Pt, Pd, Os, Ru, Ir, Rh and Au were determined by AAS, catalytic colourimetry (COL), catalytic polarography (POL), atomic emission spectrometry (AES), ICP-MS and NAA. Recently, the GPt1-7 samples were approved as national primary CRMs by the State Bureau of Technical Supervision of China.     

New Series of Rock and Sediment Geochemical Reference Materials

Certified or reference values for sixty six to sixty seven elements and element oxides are given for geochemical reference materials recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), including limestone (GSR-13), granitic gneiss (GSR-14), amphibolite (GSR-15), lake sediment (GSS-9) and stream sediments (GSD-1a, GSD-13, GSD-14). These samples supplement the GSR 1-6, GSD1-8 and GSD 9-12 certified reference materials already prepared and characterized by the IGGE.     

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.     

New Progress on Certified Reference Materials for Platinum-Group Elements: IGGE GPt-8, GPt-9 and GPt-10

Three new certified reference materials (CRM), certified for the platinum-group elements (PGE), GPt-8, GPt-9 and GPt-10 were developed based on the previous CRMs IGGE GPt-1 to GPt-7. The PGE concentration of GPt-8 is about 1 ng g^-1. GPt-9 and GPt-10 are ore samples with PGE concentrations of more than 1 μg g^-1. A multi-laboratory collaborative analysis scheme was adopted in the certification procedure, in which nine highly-experienced institutes and laboratories participated. The samples were analysed for the six platinum-group elements by nickel sulfide mini fire assay, with Te coprecipitation, and were determined by ICP-MS. Osmium was determined by isotope dilution.     

Information on Geochemical Standard Reference Materials of the CMGA Countries

This article provides information on the standard reference materials prepared in co-operation by the CMEA-countries. Among the standards are materials of technological or geochemical importance - silicates, carbonates, ores, etc. The article briefly mentions the technology of their preparation, homogeneity control, analyses evaluation and certification used for these materials. It surveys the finished and planned SRM's. The last table gives the names of foreign trade companies in the individual CMEA-countries which are entrusted with the sale of the standard reference materials produced in that particular country.     

Certified Reference Materials of Copper, Lead and Zinc (Silver) Ore Rocks and Their Concentrates (GSO 1-7)

Sulfide mineral certified reference materials GSO 1-7, recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), were analysed by twelve laboratories. Various reliable analytical methods based on different principles were adopted and classical chemical methods were taken as the primary analytical methods, by which 5729 determinations were carried out, 1425 average data were obtained, and twenty one to twenty seven elements and components were certified.     

Some Observations on the Determination of Gold and the Platinum-Group Elements in Black Shales

This research compares various ways of applying oxidative chemical decomposition to the analysis of gold-bearing black shale ores from the Russian Natalka and Sukhoj Log deposits. This study was conducted as part of the certification program for the Russian candidate black shale reference materials SLG-1 and SCHS-1 and also because of the paucity of data available on the determination of the platinum group elements (PGE) in analogous sample types. We report direct evidence of PGE volatilisation from black shale materials when processed in the presence of oxygen. We also developed a comprehensive analytical scheme for the quantitative determination of PGE in all phases (gaseous and ash) produced during slow combustion of carbonaceous materials in oxygen.
This study has shown that during combustion in oxygen at 600 °C, PGE contained in the Natalka black shale ores are lost as gaseous reaction products. Thus, the volatilized PGE (recovered in traps) account for up to 14% Pt, 40% Pd, 40% Ru and 10 % Ir relative to their total concentrations in a carbonaceous concentrate. It was also established that in the process of combustion, Au quantitatively remains in the ash cake.
In order to avoid the deleterious effects of oxygen on the volatility of the PGE, we propose a new comprehensive sample decomposition method based on the application of fluoroxidants such as BrF₃ and KBrF₄. This method was validated using samples of black shale ores and their processing products by comparing our results with those obtained independently using sealed autoclave processing of the same materials. It was shown that PGE in black shale ores and their processing products not only exist in commercially exploitable quantities but that a small proportion of PGE compounds are soluble in alcohol. We propose that in gold-bearing black shale ores, PGE are present as organometallic compounds.     

Preparation and Certification of High-Grade Gold Ore Reference Materials (GAu 19-22)

Two types of gold deposit with both good homogeneity and a high-grade of gold were selected to prepare four gold ore reference materials (GAu-19,GAu-20,GAu-21 and GAu-22) by the Institute of Geophysical and Geochemical Exploration (IGGE),China.Seven laboratories participated in the certification programme. Volumetric methods for GAu19-21 and atomic absorption spectrometry for GAu-22 were used for the homogeneity testing,the coefficient of variation being found to be less than 3%.After sample digestion and preconcentration,the samples were analysed by flame atomic absorption spectrometry (AAS),colorimetry,neutron activation analysis (NAA)and volumetric analysis. The certified values for the gold concentration in GAu19-22 are 18.3 μg g -1, 32.3 μg g -1, 53.0 μg g -1 and 5.72 μg g -1,respectively.     

New Series of Soil Geochemical Reference Materials (GSS 10-16) from the Main Overburden Region in China

Seven soil geochemical certified reference materials (CRMs) GSS 10-16 recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), are mainly used for sample analysis in geochemical surveys of the overburden region in China. Fifteen Chinese institutes and central laboratories, which operated at a high level of analytical performance analysed these samples. More than ten reliable analytical methods based on different principles of measurement were adopted, of which ICP-MS, ICP-AES and NAA were taken as the primary analytical methods. In total, 23715 determinations were carried out, 5660 average data sets were obtained, seventy two elements and components were determined and certified values of sixty nine elements and components were assigned. Rhenium concentrations were measured by isotope dilution ICP-MS in GSS-10, GSS-13, GSS-15 and GSS-16. Certified values of elements in GSS 10-16 have good precision and for 90% of these values relative uncertainties are less than 10%.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

Trace Element Data for Gold, Iridium and Silver in Seventy Geochemical Reference Materials

New concentrations for Au, Ir and Ag obtained by instrumental neutron activation analysis are presented for seventy geochemical reference materials. Results in agreement with literature values for Au and Ir down to concentrations of a few ng g⁻¹ were obtained. For Au and Ir concentrations above 10 ng g⁻¹, the repeatability of replicate analyses of reference materials was mostly better than 10%. For concentrations between 1 and 10 ng g⁻¹ the RSD for Ir was 10–30%, whereas for Au it was higher and more variable (20–50%). In addition, concentrations for Cd and Hg are presented for some of the same reference materials. The high RSD at relatively high concentrations seen in gold for some RMs (e.g., WMG-1, WMS-1) did not exist for Ir and suggests homogeneity for this platinum-group element at the sub-sample size used in this study. For the following eight RMs, mostly ultramafic rocks (CHR-Pt+, OREAS-13P, OREAS-14P, PCC-1, UMT-1, WMG-1, WMS-1, WPR-1), Ir measurements agreed within ± 10% of mostly certified or recommended concentrations, which ranged from 2 ng g⁻¹ to 6 μg g⁻¹. For the reference material UB-N, iridium concentration compared favourably to published results obtained by isotope dilution ICP-MS methods and a previously unrecognised heterogeneity is inferred for Au, Hg and Sb, but not for the other measured elements.     

Analyses of the United States Geological Survey Geochemical Exploration Reference Samples GXR-I to - 6

Analyses of the United States Geological Survey geochemical exploration reference samples (GXR) 1–6 are reported for 36 elements and compared with published values.     

中国东部地壳元素丰度与岩石平均化学组成研究

迄今我们习用的地壳化学元素丰度和岩石平均化学组成的文献值大多是收集的汇编数据,不少微量元素特别是贵金属等难测元素的丰度所依据的样品的代表性和测试质量难以考证,其值存在着颇大的不确定度。本研究立足于实测资料,在中国东部系统采集了各类火成岩和变质杂岩体及各时代的标准地层剖面岩石样品28253个,组合成2718个分析样。采用中子活化等15种可靠分析方法测试,以国家一级标准物质作质量监控。求得的华北地台地壳、中国东部上地壳和出露地壳及各类岩石的78种化学元素丰度,显著改善了地壳和岩石的化学元素丰度,填补了多种岩石微量元素丰度的空白。     

High‐Precision Sr‐Nd‐Hf‐Pb Isotopic Composition of Chinese Geological Standard Glass Reference Materials CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 by MC‐ICP‐MS and TIMS

To assess the homogeneity of and provide the first Sr‐Nd‐Hf‐Pb isotopic reference values for the Chinese Geological Standard Glasses CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5, we measured these isotopes in several measurement sessions over the course of nearly 3 years. The results were obtained by high‐precision MC‐ICP‐MS and TIMS. Our investigation indicates that these CGSG glass reference materials are homogenous with regard to Sr‐Nd‐Hf‐Pb isotopic distribution and are therefore suitable geochemical materials for Sr‐Nd‐Hf‐Pb isotope measurements. Clear differences in Sr‐Nd‐Hf‐Pb isotopic composition were observed between the glasses and the original powdered rock reference materials (CGSG‐2 and GSR‐7, and especially CGSG‐5 and GSR‐2) because of flux addition during preparation of the glasses. The new Sr‐Nd‐Hf‐Pb isotope data provided here might be useful to the geochemical community for in situ and bulk analysis.     

水系沉积物标准物质研制

为满足区域地球化学调查及矿产勘查的需要,新研制了15个水系沉积物标准物质,其中6个样品是原有水系沉积物标准物质的复制,9个新研制的样品主要采自中国北方的森林沼泽和干旱荒漠特殊景观区。样品粒度依据区域地球化学调查规范的要求,森林沼泽区采样粒级为2.0～0.22 mm,干旱荒漠区采样粒级为4.76～0.90 mm,山区和丘陵地区的采样粒级为小于0.22 mm。样品在室内晾干后在110℃烘24 h,置于大型高铝瓷球磨机粉碎并混匀,使样品中小于0.074 mm的部分大于99%以上。样品采用波长色散X射线荧光光谱进行进行均匀性检验,方差检验的F值小于临界值,所有元素的RSD均小于4%,大部分元素的RSD小于3%,P、Mn、Ti、Fe2O3、K2O等元素的RSD小于1%,证明样品均匀性良好。经2年内4次分析,检验结果表明对所检验的元素和成分均未发现统计学意义的明显变化,证明样品的稳定性良好。采用多家家实验室用不同原理的方法联合定值,邀请全国15家有资质的实验室采用准确度较高的方法分析测试约72种组分,根据ISO导则35和国家一级标准物质研制规范的要求,计算15种水系沉积物标准物质中72种元素和组分的标准值(部分组分给出参考值)和不确定度,这些新研制的标准物质是原有水系沉积物标准物质的一个补充。     

重晶石矿石成分分析标准物质研制

研制了7个重晶石矿石成分分析标准物质。其中,GSO-1为铁矿型重晶石,GSO-2、GSO-3为萤石型重晶石,GSO-4、GSO-5为石英型重晶石,GSO-6为硫化物型重晶石,GSO-7为黏土型重晶石。样品采用陶瓷衬里的球磨机加工,加工后样品粒度达到-0.074 mm。采用X射线荧光光谱法检验了钡、铜、铅、锌、锆、铝、硅、铁和钙共9种元素的均匀性,并进行振动试验。8个实验室参加定值工作,提供了硫酸钡、氧化钡、三氧化硫和锶的7个标准值,全三氧化二铁的2个标准值,氟化钙的1个标准值及铜、铅、锌和水溶盐等标准值或参考值。2009年4月,7个样品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,编号为GBW 07811~GBW 07817。     

红旗岭矿床茶尖矿区铂族元素地球化学特征及其意义

以红旗岭铜镍硫化物矿床茶尖矿区1号和9号岩体为研究对象,进行了岩石化学特征分析、微量元素分析和稀土元素（REE）分析,重点研究了其铂族元素（PGE）地球化学特征。REE分析结果表明,岩石富集轻稀土元素,且有微弱的铕负异常。PGE富集在硫化物含量高的岩石中,与硫化物含量呈正相关关系。岩石中PGE分异明显,富集Rh、Pt和Pd。推测该区的基性-超基性岩形成于硫不饱和玄武质岩浆的演化,岩浆有地壳物质混染的特征,其成矿物质来源于上地幔,主要成矿机制为深部熔离-贯入作用。     

Mineralogical Associations of Arsenic and Antimony in Thirty Five Geochemical Reference Materials by Sequential Extraction with Hydride Generation and Atomic Absorption Spectrometry

A method is described to estimate the chemical forms of arsenic (As) and antimony (Sb) in a variety of geochemical reference materials, combining a sequential extraction scheme with hydride generation and atomic absorption spectrometry (HG-AAS). The fractions dissolved by sequential extraction are empirically defined as the exchangeable, EDTA soluble, oxide, sulfide and residual fractions. The amount of As and Sb in the EDTA soluble fraction have been derived mainly from oxide phases, and partly from carbonate minerals. Most sulfide minerals in common geological samples were considered to be dissolved with the digestion of 0.7 mol l⁻¹ NaOCl, but only small fraction of arsenopyrite and loellingite in ores could be dissolved in this way. Satisfactory agreement was observed between the sum of the As or Sb values from exchangeable to residual fractions and the reported total As or Sb values, with a few exceptions. Analytical results of As and Sb for thirty five geochemical reference materials are tabulated, and geochemical and mineralogical features are discussed.     

标准物质数据处理及定值的MPDPS软件

本文详细介绍了由六个功能模块组成的多参数标准物质数据处理及定值软件MPDPS。软件除了对标准物质进行定值处理外,还能对测试数据进行多方面的统计处理。文中结合对GSR7-126个标样数据处理及定值的实例介绍了MPDPS的各项功能。用MPDPS对这6个标样定值的结果较为满意。