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地质标准物质是保障地质样品分析结果准确性的重要基准。目前,一级地质标准物质数量居十三大类首位,形成了具有国际影响力的地质标准物质体系。本文依据基体类型和定值特性,将一级地质标准物质划分为基础、矿石、海洋、环境、能源和特殊用途等六类,总结了各类标准物质的研制数量、特点、定值指标、应用范围及意义。针对现阶段数量众多的地质标准物质在应用中还存在研制数量少、系列化不足、基体类型单一、定值指标少等问题,本文分析了不同类型存在的具体问题及产生的原因,探究研制技术成熟的地质标准物质中仍有多种成分难定值以及定值方法单一的可能原因,重点讨论了标准物质研制技术中影响定值水平的细节问题：(1)阐述了均匀性检验测量方法的优缺点,XRF法以其高精密度的优势应用于均匀性检验值得关注和研究;(2)提出了考虑元素性质、含量级次兼顾测试技术评定均匀性未检元素的不确定度评定方法;(3)分析了稳定性不确定度在总不确定度构成中成为主要贡献量的原因是当前的计算方法造成的,有待于进一步研究合理的评定方法;(4)建议针对不同类型标准物质,制定相对扩展不确定度控制限以获得准确可靠的标准值。结合当前地质标准物质存在的不足和工作需求,本... 相似文献
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激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)适合于直接分析硫化物矿物中痕量元素的含量及空间分布,但硫化物矿物的激光剥蚀特性与硅酸盐及氧化物不同,受到的干扰也更严重,且由于硫化物标准物质(尤其是含铂族元素、Au、Ag等贵金属元素标准物质)极度缺乏,限制了LA-ICP-MS技术在硫化物微区分析中的广泛应用。本文以贵金属标准样品GPT-9和矿石标准物质为原料合成锍镍试金扣,并封入真空管中重熔,利用背散射电子图像和LA-ICP-MS分析元素分布的均匀性,探讨真空重熔锍镍试金扣制备硫化物原位微区分析标准样品的可行性。背散射电子图像(BSE)显示真空重熔后锍镍试金扣由单相S、Ni化合物组成。LA-ICP-MS线扫描和点扫描分析表明,锍镍试金扣中S、Ni、Cr、Co、Cu、Pb、Sb、Cd、Bi等主量及微量元素分析精密度(RSD)均小于10%,均匀分布;在镍扣制备过程中Zn相对于Cu、Pb、Sb更难进入硫化物相;贵金属元素Au、Ag、Pt均一性较好,其余贵金属元素由于含量低、仪器波动及质谱干扰等影响因素造成分析数据的RSD相对较大,但可通过提高原料中贵金属元素含量、降低熔融样品淬火温度等方法进一步提高其均匀性。锍镍试金扣的组成元素对铂族元素分析的质谱干扰研究表明,重铂族元素(Os、Ir、Pt)和Au受到的干扰可忽略不计;轻铂族元素(Ru、Rh、Pd)受金属氩化物干扰较为严重,需进行干扰校正。研究认为,真空重熔技术可有效提高锍镍试金扣中各元素(包括贵金属)的均一性,达到硫化物原位微区分析标准样品的要求,利用真空重熔锍镍试金扣制备LA-ICP-MS原位微区痕量及贵金属硫化物分析标准样品具可行性。 相似文献
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硫化物矿物中痕量元素的激光剥蚀-电感耦合等离子体质谱微区分析进展 总被引：10，自引：3，他引：7
第一行过渡金属元素及痕量贵金属元素高度富集在硫化物矿物中,常形成具有工业意义的矿床,使得硫化物具有重大的经济价值。对天然硫化物矿物中的这些痕量金属元素丰度及其分布的研究,在矿石成因学、经济地质学、环境地球化学等领域具有重要的应用价值。激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)微区分析技术是一种强大的痕量元素分析工具,非常适合直接分析硫化物矿物中痕量元素的浓度及其空间分布。由于硫化物的激光剥蚀特性与硅酸盐及氧化物不同,分析校准用的标准物质又极度缺乏,严重阻碍了这一技术在硫化物矿物微区分析中的应用。本文评述了硫化物简介、硫化物中痕量金属元素分析的意义、LA-ICP-MS微区分析技术在硫化物矿物痕量元素分析中的优势及近年来的应用进展、硫化物分析中的干扰与校准、包含铂族元素及金的硫化物标准物质的研制进展及合成硫化物标准物质最有应用前景的方法。 相似文献
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CGSG系列标准物质元素分馏效应及主量微量元素单元内均匀性探究 总被引：2，自引：2，他引：0
探究CGSG系列标准物质(CGSG-1、CGSG-2、CGSG-4、CGSG-5)的元素分馏效应及均匀性问题有助于开展其质量评估和应用推广。本文采用电子探针(EMPA)和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)研究了CGSG标准物质中的元素分馏效应、主量和微量元素单元内均匀性,并报道了主量和微量元素分析数据。结果表明,在50μm激光束斑下,CGSG系列标准物质的元素分馏效应可忽略不计。EMPA均匀性指数结果显示,CGSG标准物质主量元素的单元内均匀性满足要求;以MPI-DING标准物质为参照,LA-ICP-MS测试CGSG标准物质中的大多数微量元素的单元内均匀性良好。与已报道的数据相比,本文报道的EMPA主量元素数据偏差在2%以内;LA-ICP-MS主量元素数据偏差在5%以内,微量元素数据基本匹配,少数元素由于分析不确定度较大等原因,如Cr、Ge、Cd、As、Tl等与已报道数据偏差较大。总体上,本文报道的分析数据可为CGSG定值数据库提供进一步的补充。 相似文献
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均匀性检验是环境标准样品研制的重要技术环节,在均匀性检验过程中,数据漂移对环境标准样品均匀性判定及其不确定度评定的影响不容忽视。本文结合实例,从实验方案和数理统计方法等方面探讨了随机分析法、随机区组法、内插校正法、趋势分析校正法等均匀性检验实验方案及数据漂移校正方法。提出采用t检验法判断数据漂移的显著性,在数据漂移趋势不显著的情况下,采用随机分析法进行标准样品的均匀性检验。在数据漂移显著的情况下,宜采用内插校正法或趋势分析校正法对均匀性数据进行漂移校正。以某土壤中Ni元素均匀性检验为例,经采用内插校正法和趋势分析校正法校正漂移数据后,测量值的相对标准偏差(RSD)由3.0%分别下降为1.4%和1.2%,直线模型斜率的绝对值由0.2003 mg/kg分别下降为0.02870mg/kg和4.709×10~(-5)mg/kg。土壤中Ni、Cu、Co、Tl等4种重金属元素的瓶间均匀性不确定度分量(u_(bb))与随机分析法相比,下降最高达78%。在长时间分析测试过程中数据漂移校正效果欠佳的情况下,宜采用随机区组法进行标准样品的均匀性检验。 相似文献
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岩矿石地质标准物质研制中的几个问题 总被引：1，自引：0，他引：1
近十余年，中国在岩石、矿石、地质标准物质研制方面取得了显著成就。鉴于岩石、矿石、地质物料组成复杂、定值项目较多、研制难度较大的实际情况，工作中应结合物料特点，妥善解决标准物质的稳定性、均匀性、量值准确性这三个关键问题 相似文献
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Wenjun Li Jing Wang Mengmeng Cui Xia Liu Lihui Jia Kaiyun Chen Shitou Wu Bingyu Gao Dingshuai Xue Yanhong Liu Chao Li Yang Luo Benxun Su 《Geostandards and Geoanalytical Research》2023,47(1):199-210
Two clinopyroxene megacrysts, DMP-2 and DMP-3, were collected from Cenozoic alkali basalts in the Hannuoba region of China. They were characterised for major and trace element compositions for in situ microanalysis. EPMA and LA-ICP-MS analyses indicate homogeneity in the element mass fractions in both clinopyroxene samples. Bulk analyses using various techniques (XRF, ICP-OES and solution ICP-MS) also reveal good consistency in their major and trace element data. They, thus, can be used as potential reference materials for elemental in situ microanalysis. Accordingly, element mass fractions are recommended for thirty-two elements. 相似文献
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Dongyang Sun Jin Liu Chenzi Fan Linghao Zhao Xiuchun Zhan Mingyue Hu 《Geostandards and Geoanalytical Research》2023,47(1):7-22
Four CGSP (Chinese Geological Standard Powders) carbonate matrix element reference materials were prepared by a coprecipitation method. The major and trace elements were dissolved from natural rare earth carbonate raw materials in strong acid and precipitated with ammonium bicarbonate or ammonia to form carbonate matrix phases. The carbonate reference materials were ground and pressed into tablets for microanalysis. The element homogeneity and stability in CGSP reference materials were tested by LA-ICP-MS using a calibration strategy without an internal standard element and evaluated mainly following ISO Guide 35: 2017 and JJF 1343-2012. Although the homogeneity of most of elements in the CGSP series were comparable to the repeatability obtained from homogeneous glasses, some elements (e.g., Mo, Se, Ga, Ge, Cd, Ni, Co, U) were found to have some degree of heterogeneity. All of elements passed the t-test evaluation in a 32-month stability examination except for Mo in CGSP-A, Na, Ge, Mo in CGSP-B, Ni, Cd, Sn in CGSP-C, and Al, P, Tb, Ho in CGSP-D. The certified element mass fraction values and uncertainties were determined with the characterisation of a non-operationally defined measurand using various bulk analysis methods in eight laboratories. GGSPs will provide a new carbonate calibration reference option for microanalysis. 相似文献
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激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）副矿物U-Th-Pb定年技术为精确厘定地质演化历史、探讨成岩成矿等重要地质作用过程提供重要的时间参数,是地质年代学快速发展的重要技术支撑.总结了LA-ICP-MS副矿物U-Th-Pb定年技术在元素分馏校正、非基体匹配分析、标准样品研发、普通铅校正、高空间分辨率及高效率分析等方面取得的重要进展.展望未来,需更进一步深入探讨和研究元素分馏及基体效应机理,研发更多种类的高质量副矿物标样,建立更多更准确、更精密、更高空间分辨率及更高效的LA-ICP-MS副矿物U-Th-Pb定年新方法和新技术,以实现从更微观和更精细的角度探讨地质问题,并持续为高效解决地球与行星科学研究领域重大科学问题提供关键支撑. 相似文献
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Magne Ødegård 《Geostandards and Geoanalytical Research》1999,23(2):173-186
This paper describes a technique for the preparation of synthetic calibration materials for use in laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and other microtechniques for mineral analysis. The method is based on direct fusion in high-purity graphite electrodes, and the requisite temperatures for melting are obtained by resistance heating using a welding rectifier as the power source. The technique has been tested on quartz (SiO2) and rutile (TiO2) for a relatively large range of elements, including all the rare earth elements. Different starting materials for preparation of calibration materials were studied, and it is shown that many natural materials form separate phases during fusion, resulting in unusable calibration materials for microanalysis. However, calibration materials prepared fully synthetically from oxides and/or element nitrates in solution were found to be of good homogeneity, and this preparation technique was used throughout in this work. The quality of the calibration materials for quartz and rutile was assessed by LA-ICP-MS, using Si and Ti as internal standard elements respectively. The NIST SRM 612 and 614 glass standards were used to assess the accuracy of the calibration materials for quartz. Calibration curves based on two independently prepared sets of calibration materials and the two NIST glasses are shown for a number of elements, demonstrating excellent agreement between the NIST glasses and the synthetically prepared quartz glasses. Vesicles are shown to form in the SiO2 glasses, but this does not influence their value as calibration materials, provided that a reference element is used as an internal standard. The advantages of fusion in high-purity graphite electrodes are emphasised, particularly the very high sublimation point of graphite, its very high state of purity, the very short melting and quench time, the speed and simplicity of the method, and the low risk of introducing impurities. Extension of the method to other minerals and applications is discussed. 相似文献
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矽线石成分分析标准物质研制 总被引：1，自引：0，他引：1
随着矽线石应用领域的逐步拓展,英国、南非和日本等国家已研制了4种矽线石标准物质,而我国仅有一种矽线石国家二级标准物质,无论从组分的浓度梯度范围还是定值指标等方面,均难以满足我国研究需求。本文针对我国矽线石的分布情况,在黑龙江林口县和河南内乡县采集典型矽线石原矿2种,在黑龙江林口县采集矽线石精矿1种,按照国家一级标准物质研制标准和规范要求,研制了3种矽线石成分分析国家一级标准物质(批准编号为GBW07843、GBW07844、GBW07845)。均匀性检验结果表明,除个别指标(Y-1的TFe_2O_3、Cu和J-1的Mn O等)外,3种标准物质检测指标的F值均小于临界值F0.05(24,25)=1.96,组内和组间无明显差异;Y-1的TFe_2O_3、Cu和J-1的MnO等指标的组内和组间差异主要来源于分析方法误差,由此表明此批标准物质均匀性良好。在14个月考察期内,3种标准物质计算得到的拟合直线斜率b1均不显著,表明3种标准物质有较好的稳定性。经我国10家实验室使用多种分析方法对矿石中的主量元素、痕量元素和矽线石含量(硅铝,SAl_2O_3)等共计39种组分联合定值,各组分的相对扩展不确定度处于0.60%~29.9%区间,3种矽线石标准物质主量成分Al_2O_3的含量分别为25.85%、28.16%和55.06%。该系列矽线石标准物质可满足地质、环境等研究领域相关样品分析质量监控工作的需求。 相似文献
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(InstItute of Rock Mineral Analysis Ministry of Geology Mineral Resources Beijing ) 《岩矿测试》1995,(2):81-113
研制的黄铁矿、黄铜矿、方铅矿和闪锌矿４个标准物质是国内首次成功研制的硫化物矿物成分分析标准物质。样品采用重选、磁选和电磁选等选矿技术提纯矿物，获得纯度大于９５％的单矿物样品。黄铁矿和闪锌矿用棒磨机少量多级粉碎至０．１４７ｍｍ，方铅矿和黄铜矿用小型玛瑙球磨机粉碎至０．０９７ｍｍ。经单因素方差分析检验，均匀性符合要求。采用小包装在干燥、充氩气气氛中保存样品，使样品稳定性有足够保证。连续４年定期监测了样品中全硫含量，证明稳定性良好。样品由国内经计量认证的５家实验室采用多种分离富集手段、不同原理方法协同分析。标准值的确定依据数据分布特征而定，对于服从正态分布的元素，用算术平均值作为定值，对不服从正态分布的元素用多参数模式定值。共确定了５６个标准值，１６个参考值，６个信息值。该批标准物质于１９９４年１２月通过了国家标准物质研究中心组织的专家复审，并于１９９５年４月被国家技术监督局批准为国家一级标准物质，标准号分别为ＧＢＷ０７２６７（ＧＳＭ－１）、ＧＢＷ０７２６８（ＧＳＭ－２）、ＧＢＷ０７２６９（ＧＳＭ－３）、ＧＢＷ０７２７０（ＧＳＭ－４）。 相似文献
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《Chemie der Erde / Geochemistry》2014,74(3):375-384
Homogeneity testing of candidate reference materials requires distinguishing the effects of measurement uncertainty of the analytical method from true compositional variations within the material. Many in situ microanalytical techniques do not allow classical ANOVA homogeneity testing due to the infeasibility of truly replicated analyses on the same analysis volume. This also applies to the analysis of beam-sensitive and light element-bearing materials by electron probe microanalysis (EPMA). This reality has led me to reconsider the homogeneity index approach used in the testing of microanalytical reference materials by EPMA. Based on statistical considerations, I show that the homogeneity index is suitable for statistical significance testing using F and chi-squared statistics and allows estimating the contribution of compositional heterogeneity to the total uncertainty budget of the referenced values. However, there are problems of bias and masking of small compositional variations by measurement uncertainty. This contribution shows the strong impact of the total number of measurements on the resolution of a microanalytical homogeneity study and discusses how to quantify the relative contribution of heterogeneity to the total uncertainty budget. I present an example of EPMA to illustrate this approach and show some pitfalls and limitations in its application. 相似文献
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钼矿石与钼精矿成分分析标准物质研制 总被引：2，自引：2，他引：0
钼矿勘查开发与综合利用评价等工作需对其化学成分进行准确测试,标准物质可为分析测试提供基础标准和技术支撑。我国已有的钼矿石和钼精矿标准物质系列性不足,且余量不多,多数样品已耗尽。本文为满足钼矿资源勘查、开发与贸易的总体需求,研制了3个钼矿石和1个钼精矿成分分析标准物质。根据设计的钼含量的梯度范围和钼矿的矿床成因,在钼矿资源储量最多的河南省采集了1个钼尾矿(Mo含量0.02%)、1个钼矿石(Mo含量0.09%)和1个钼精矿(Mo含量50.0%)。3个钼矿石采用重量法组合制备的方式加工,1个钼精矿为原样粉碎加工,钼精矿在加工制备过程向球磨机内充氩气保护,防止硫化物氧化。按照一级标准物质研制规范,采用13家实验室使用多种准确可靠的方法共同定值,定值元素包括成矿元素(Mo),可综合利用元素(W、S、Cu、Pb、Zn、Fe、Bi),具找矿和矿产评价意义的微量元素(Ag、As、Cd、Mn、P、Pb、Sb)及构成脉石的主成分(SiO2、Al2O3、Fe2O3、CaO、MgO、Na2O、K2O)共计26种。3个钼矿石标准物质Mo的含量分别为0.066%、0.15%、0.54%,1个钼精矿标准物质Mo的含量为50.08%,是已有标准物质的良好补充和完善。标准物质经均匀性和稳定性统计检验具有良好的均匀性和稳定性;标准值计算方法正确,不确定度评定合理,经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 07141~GBW 07144),可用于钼矿的勘查、开发、选冶及贸易中化学成分测试的量值标准与分析质量监控。 相似文献
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Trends in Analytical Developments and Earth Science Applications in LA-ICP-MS and LA-MC-ICP-MS for 2004 and 2005 总被引：1，自引：0，他引：1
Paul J. Sylvester 《Geostandards and Geoanalytical Research》2006,30(3):197-207
This review of laser ablation-inductively coupled plasma-mass spectrometry includes research that employed quadrupole instruments, and single-collector and multicollector magnetic sector field instruments. The most important trend in 2004–2005 was the growing appreciation that small matrix effects in LA-(MC)-ICP-MS need to be addressed in order to produce highly precise and accurate data by the method. The issue is most acute for isotope ratio measurements that require standard-sample-standard bracketing but can also be important for certain elemental analysis. Matrix-dependent elemental and isotopic fractionations were studied from the standpoint of laser-sample interactions and the behaviour of laser-generated particles in the ablation cell, transfer tubing and ICP torch. Innovations in LA-(MC)-ICP-MS involved signal smoothing, in torch laser ablation, on-line isotope dilution and molecular oxide monitoring. Other important research was carried out on the calibration and homogeneity of various reference materials; and the exploration of mature ( in situ U-Pb geochronology) and emerging (apatite fission-track chronometry, U-Th/He thermochronology, boron/strontium/uranium-series isotopic microanalysis) applications in the Earth sciences. 相似文献
20.
Monica E. Erdman Cin‐Ty A. Lee Wenbo Yang Lynn Ingram 《Geostandards and Geoanalytical Research》2014,38(1):51-60
With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials. 相似文献