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。     

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%.     

The Preparation and Characteristics of the Geochemical Certified Reference Material BEM (Emeishan Basalt)

A basaltic certified reference material BEM, prepared by Chengdu University of Technology, has recently been approved as a Primary Grade Reference Material (GBW07126) by the General Administration of Quality Supervision, Inspection and Quarantine of China. BEM was sampled from the Emeishan Basalts in China, which is one of the largest basalt provinces in the world. After successfully completing homogeneity and stability tests, collaborative analyses were carried out in seventeen Chinese institutes and laboratories and two American laboratories. More than ten reliable analytical methods based on different principles of measurement were adopted, of which ICP-MS, NAA and ICP-AES contributed 60.5% of all results. Fifty-four elements and oxide components were characterised as certified values, four elements as recommended values and nine elements as information values. A minimum sampling mass of 40 mg for most elements is recommended for use.     

Report on the 2007 Recertification of the Certified Reference Materials GAS (Serpentinite) and OShBO (Alkaline Granite)

A report is presented on the recertification of two certified reference materials (CRMs) initially prepared and certified by the Central Geological Laboratory of Mongolia (CGL), namely serpentinite GAS and alkaline granite OShBO. Subsequent work done in collaboration with the International Association of Geoanalysts (IAG) followed the International Organisation for Standardisation (ISO) guidelines for certification (ISO Guide 35, 2006) more closely than had been possible originally. The certification protocol followed was that of the International Association of Geoanalysts (IAG). The recertification added to the number of elements that were certified for OShBO (from 21 to 30), but not for GAS (decreased from 15 to 12) because of the greater analytical difficulties posed by that sample matrix in meeting the more stringent metrological requirements for recertification. Further, the uncertainties for these values were established in accordance with the Guide to Measurement Uncertainty ; individual contributions of heterogeneity and bias are reported as appropriate for each of the certified constituents. Traceability of the certified values was demonstrated to the greatest possible extent, based on concurrent analyses of the matrix-matched existing CRMs, SW and GM, by all participating laboratories. The materials are now available from the CGL for use by laboratories in controlling data quality when analysing materials of similar matrices.     

银-二乙基二硫代氨基甲酸钠法测定铁矿石中砷溶样方式的改进

改进了铁矿石样品溶解方法，尝试用硫-磷混酸溶解铁矿石样品，缩短了分析时间，提高了分析精度。溶解后的样品以银-二乙基二硫代氨基甲酸钠法（Ag—DDTC）用于部级标准物质测定，砷的测定结果与标准值相符；用于碱性矿石如球团样品中砷的分析，多名操作者的测定结果吻合。     

Usable Values of Nickel Ore and Nickel Concentrate Certified Reference Materials

The preparation and characterisation of three nickel ores and two nickel concentrate certified reference materials are described in this paper. The samples of nickel ore and nickel concentrate were collected from the Hongqiling nickel deposit in Jilin province. The raw materials were crushed and passed through a 2.0‐mm sieve. The rough samples were then ground for 48 hr in a high‐alumina ball mill to a final size of < 0.074 mm. Homogeneity of the samples was tested by X‐ray fluorescence spectrometry (WD‐XRF) and inductively coupled plasma‐atomic emission spectrometry (ICP‐AES). The relative standard deviations (RSD) of results on mass fraction measurements by WD‐XRF were < 1.0% m/m for eighteen components. F‐tests showed that all five samples were homogeneous. Nineteen laboratories contributed with measurement results (2127 in total) for the certification of mass fractions for twenty‐three elements and compounds. Twenty‐three components in the nickel ores and twenty components in the nickel concentrates were characterised as certified values, while the Ni mass fractions ranges from 0.1 to 9.02% m/m in these certified reference materials. These five samples were approved as national certified reference materials by the National Organisation of Reference Materials of China in 2012.     

汞分析仪直接测定矿石中的痕量汞

使用汞分析仪直接对不同矿石中的痕量汞进行快速准确测定。矿样直接称样后,无需复杂的湿法消解或样品前处理,6 min内即可完成汞的测定。建立的方法不受样品性质影响,无基体干扰,方法回收率为90.0%～109.0%,检出限为0.60 ng/g,相对标准偏差(RSD,n=8)为0.95%～4.74%。使用该法分析了6大类矿石标准参考物质和实际样品,并与常规方法进行比较,分析结果与证书值和其他方法测定值一致。与现行国家标准分析方法相比,该方法大大缩短了分析周期,适合大批量试样的分析。     

锗矿石和铟矿石化学成分分析标准物质研制

目前国内外没有以稀散元素锗、铟为特征元素的矿石标准物质,为了满足我国地质找矿的需求,本文采集广东省韶关凡口铅锌矿作为锗矿石候选物,广西南丹铜坑铅锌矿作为铟矿石候选物,依据国家一级标准物质技术规范,由10家实验室采用化学分析方法和现代仪器分析方法协作定值,研制了1种锗矿石标准物质(GBW07831)和1种铟矿石标准物质(GBW07833)。锗矿石标准物质定值组分为45项,铟矿石标准物质定值组分为47项,包括特征元素、共存元素、稀土元素(15项)、造岩元素和痕量元素,其中锗矿石中锗含量为21.6×10-6,铟矿石中铟含量为39.7×10-6。研制的2种标准物质丰富了我国矿石标准物质的种类,可用于锗、铟矿石化学成分分析测试的量值标准和日常质量监控。     

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.     

生物成分系列标准物质的研制

GSB系列生物标准物质包括大米、小麦、玉米、黄豆、圆白菜、菠菜、茶叶、奶粉、鸡肉和苹果等10种生物样品，用冷冻干燥等技术制备。由14个分析水平较高的实验室协作，采用等离子体质谱、等离子体光谱和仪器中子活化为主的10余种分析方法测试，共进行了22477次测定，取得了5136组平均值数据，定值元素59种，定标准值元素54种。     

熔融制样X射线荧光光谱法测定铜矿石中16种主次量元素

铜矿石类型繁多,矿石赋存状态各异,成分复杂。在现有的铜矿石熔融制样X射线荧光光谱（XRF）分析方法中,选取标准物质个数和矿石类型少、分析范围宽,与实际样品类型相差太大,且制备的熔融片质量不高。本文选用铜含量既有良好浓度变化范围,又符合铜矿石常见含量的包括铜金银铅锌钼铜镍等各类矿石的24个标准物质,以四硼酸锂-偏硼酸锂-氟化锂为混合熔剂,熔剂与样品质量比为30：1,以溴化锂为脱模剂,改进样品预处理方式,将通常采用样品预氧化后或熔融中加入脱模剂的方式,改进为加入脱模剂后再用混合熔剂完全覆盖的方法制备了高质量的熔融片,建立了XRF测定铜矿石中铜锌铅硅铝铁钛锰钙钾镁钼铋锑钴镍16种元素的分析方法。分析铜矿石国家标准物质GBW 07164、GBW 07169,各元素的精密度（RSD）为0.1%~5.4%。分析国家标准物质GBW 07163（多金属矿石）、GBW 07170（铜矿石）的测定值与标准值相符;分析实际铜矿石样品,铜锌铅钼铋锑钴镍的测试结果与电感耦合等离子体发射光谱法和其他方法的测定值相符。本文方法扩大了基体的适应性,提高了实际应用价值。     

Comparison of Synchrotron Radiation X-Ray Fluorescence with Conventional Techniques for the Analysis of Sedimentary Samples

A comparison is made of elemental analyses of sediment samples (lake bottom sediments and sediments from the petroliferous Bazhenovka Formation) by five competitive methods (synchrotron radiation X-ray fluorescence (SR-XRF), INAA, ICP-MS, AAS and traditional XRF). The object of this study was to identify the most suitable analytical techniques for applications in sedimentary geochemistry. Advantages and shortcomings of the five techniques were considered with respect to applications related to studies of palaeo-climate changes recorded in sedimentary cores from Lake Baikal and the geochemical stratigraphy of the Bazhenovka Formation, which is rich in organic material. We have concluded that SR-XRF was the best technique for producing extensive analytical data series, from the point of view of its speed, ease of application, cost, non-destructive nature and sensitivity, which allowed for the simultaneous determination of more than twenty elements of geochemical interest in small samples of sediments. An additional benefit of the method was demonstrated when used for the independent certification of geological reference materials. International reference samples BIL-1 and SDO-1 were certified by means of this method without use of reference materials. Analyses were based on the physics of the theory of energy transport.     

大气颗粒物中含碳组分的分析技术

对国内对自20世纪70年代发展起来的大气颗粒物中含碳物质组分的多种分析技术进行了评述，介绍了国内外发展现状，阐述了当今主要分析技术的特点。     

九个铁矿石标准物质研制

采集制备了9个铁矿石标准物质,全铁含量为20.17%~66.87%,涵盖了贫铁矿至铁精矿粉,能满足铁矿勘查和选冶的需要。采用精度相对较高的测试方法进行均匀性检验,结果表明样品均匀性良好。选择13家具有丰富经验的实验室采用不同原理的方法进行定值测试,定值项目14种,其中13种组分提供标准值,H2O+提供参考值。     

常量金标准物质定值中离群值的统计识别

离群值的剔除常用数理统计的方法,如格拉布斯检验法和迪克逊检验法等,但是这些统计方法用于常量金标准物质分析结果的统计检验,都存在着对离群值剔除明显不够的问题.本文建立了以常量金重复分析相对偏差允许限为依据的离群值统计识别方法,包括统计计算待定值样品中金的算术平均值x和相对偏差允许限YG,确定合格的测定结果的数据区间,从而识别出离群值并予以剔除;一次剔除后,按照新的统计量确定下一轮的离群值剔除范围,直到无离群值后,给出金的平均值及其波动范围.以15个人工组合的常量金标准物质为例,模拟金标准物质定值分析,以密码形式分派给不同单位和分析者,共收集10套独立分析结果,采用本法剔除离群值后,所得金算术平均值与金标准参考值更加接近,其相对偏差的质量分数为0.35,达到优秀;而格拉布斯法(或迪克逊法)和中位值法的质量分数分别为0.42和0.40,只能达到良好.应用本文建立的离群值统计识别方法,质量分数等级有了明显提高,增强了数据统计分析的有效性.     

中国火成岩化学元素的丰度与分布

在中国各构造单元构选采了１０３６４件火成岩样品合成１１３１个分析样，采用仪器中子活化法，Ｘ射线荧光光谱法，原子吸收法，原子荧光光谱法，催化波极谱法和分光光度法等１５种可靠分析方法进行测试，对一些难测痕量元素采用了最新的分析研究成果，以同类国家一级标准物质监控分析质量。     

镁矿石中钙镁的快速连续测定

在一份ｐＨ１０的氨缓冲溶液中,分别用乙二醇二乙醚二胺四乙酸和环己二胺四乙酸连续滴定Ｃａ和Ｍｇ。方法用于镁矿石中Ｃａ和Ｍｇ的测定。结果与标准值和外检结果一致。测定镁矿石中ＣａＯ和ＭｇＯ１２次的ＲＳＤ分别为〈５％和〈０．３０％。