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.     

ISO Best Practices in Reference Material Certification and Use in Geoanalysis

The International Organisation for Standardisation (ISO) has published many guides, or technical standards, of great value to analytical geochemists. Two of particular importance are Guide 33 (Uses of Certified Reference Materials) and Guide 35 (Certification of Reference Materials). Both were first developed in the 1980s and undergo regular review and updating by the Reference Materials Committee (REMCO) that operates within ISO. Recent revisions have focused on adding statistical rigour to both guides. Although this offers significant advantages for use by professional metrologists, there are consequent issues of comprehension by the analytical chemists who in fact have the greatest need of them. A major focus of Guide 35 is the development of reference material uncertainties that are in full compliance with the Guide on Measurement Uncertainty (GUM), jointly issued by ISO, IUPAC and others. Guide 35 details handling of uncertainty due to (1) degradation on the shelf and in transport, (2) sample heterogeneity and (3) inter‐method and inter‐laboratory bias, as well as within‐laboratory repeatability. The International Association of Geoanalysts has developed a protocol for reference material certification that applies Guide 35 to the specific needs of the geoanalytical community. The approach being taken by the IAG in developing GUM‐compliant uncertainties for its certified values is presented. Recommendations made in Guide 33 for how a laboratory should compare its own results with certified values in assessing laboratory accuracy are outlined. Additionally, the subject of misusing reference materials is discussed. The apparent misuse occurs because so few CRMs exist that meet critical measurement needs of geoanalytical laboratories and that also meet the rigorous metrological demands of the latest editions of the ISO Guides. All of the focus of the IAG certification programme has been to undertake certifications that would fill gaps in CRM availability and thus serve to limit this misuse.     

Certificate of Analysis of the Reference Material BRP-1 (Basalt Ribeirão Preto)

Reference materials (RM) are essential to achieve traceability of measurements. Specific uses of RM in analytical laboratories are the validation of methods, the calibration of instruments, the quality control and the demonstration of proficiency. This paper describes the certification of a new geochemical reference material, named BRP-1 (Basalt Ribeirão Preto), and acts as the certificate of analysis for this RM. The rock sample was crushed and pulverised at the USGS (Denver, USA), homogenised and split into 1920 bottles, with 55 g each. BRP-1 was transported back to Brazil and the homogeneity between and within bottles was assessed to demonstrate sufficient homogeneity for certification. The chemical characterisation was performed by twenty-five laboratories. Each laboratory received two bottles of BRP-1 and one of BCR-2 (Basalt Columbia River) used for quality control (QC). Reference values and uncertainties were calculated for forty-four constituents of BRP-1, following ISO Guide 35 recommendations and the IAG Protocol. The calculation of each reference value included data of proven traceability from at least ten laboratories using two or more analytical techniques and the uncertainties combines the characterisation and between bottle homogeneity contributions.     

Experience of the International Association of Geoanalysts as a Certifying Body

Reference materials (RMs) to support geoanalysis have a long history, dating back to the issuance of G-1 and W-1 in 1951. This paper addresses only one aspect of the most recent part of that history, the experience of the International Association of Geoanalysts (IAG) as a certifying body. In 2002, the Certification Committee of the IAG met in Potsdam to discuss becoming a certifying body able to produce RMs for the geoanalytical community. Following that meeting, the IAG developed and published a protocol to assure that IAG RMs would meet International Organization for Standardization (ISO) guidelines to the fullest extent possible. Many practical problems arise in the application of the recommendations of the ISO Guides to any one specific certification project. The recommendations describe the ideal; achievable reality is always somewhat less than that ideal, presenting a significant challenge to the IAG as a certifying body. This paper will summarise experience to date, while focusing on the most challenging issues, deriving uncertainties compliant with the Guide to Uncertainty in Measurement (GUM) and establishing traceability of certified values (CVs).     

An Evaluation of Methods for Assessing the Competence of Laboratories Based on Performance in the GeoPT Proficiency Testing Scheme

The original certification protocol, published by the International Association of Geoanalysts in 2003, specified that the competence of laboratories selected as competent to contribute certification measurements should be evaluated from their performance in the GeoPT proficiency testing programme. Round 39 of the IAG GeoPT proficiency testing programme provided an opportunity to examine four methods of evaluating laboratory competence based largely on the use of proficiency testing z‐scores as performance indicators. This opportunity arose because two test materials were co‐analysed by participating laboratories in this round: a syenite, SyMP‐1, supplied by the USGS, and an established CRM, the nepheline syenite, CGL 006. The performance of laboratories was assessed in four ways; in each case, consensus values and their uncertainties as derived from selective data sets of competent laboratories were compared with results derived from the routine GeoPT data assessment, involving all submitted measurements. An overall comparison of results showed no significant statistical differences in either consensus values or uncertainties between these data sets. This conclusion was unexpected and calls into question the widely held assumption that ‘better’ consensus data would be obtained from a subset of laboratories judged to be competent on the basis of proficiency testing performance indicators.     

The GeoPT Proficiency Testing Programme as a Scheme for the Certification of Geological Reference Materials

ISO Guide 35:2017 provides, for the first time, an alternative way of characterising certified reference materials using proficiency testing. In this paper, the properties of assigned values derived from the well‐established GeoPT proficiency testing scheme are examined. This scheme, designed for laboratories that undertake the routine analysis of silicate rocks and related materials, routinely has over 100 participants contributing results. Following a detailed assessment of the metrological properties of GeoPT assigned values in relation to Guide 35 recommendations, it is demonstrated that these values may be regarded as certified values, provided a number of criteria are met. These criteria include the following: a demonstration of sufficient homogeneity of the candidate CRM; circulation, when judged to be appropriate, of an established matrix‐matched CRM for co‐analysis in that round; the robust statistical analysis of data sets using GeoPT established criteria; a decision whether assigning a value is justified (including a requirement of a minimum of fifteen valid results); and an expert group to manage the certification and the maintenance of appropriate records. In summary, the GeoPT proficiency testing scheme, subject to the arrangements summarised above, is considered to be competent for the certification of geological reference materials.     

International Association of Geoanalysts'Protocol for the Certification of Geological and Environmental Reference Materials

This protocol has been developed by the International Association of Geoanalysts to demonstrate procedures for the certification of geological and environmental reference materials to comply to the fullest extent possible with recommendations of the International Organisation for Standardisation (ISO Guide 35). A practical approach is described on the assumption that certifications will be normally be based on collaborative analysis programmes in which participating laboratories are preselected on the basis of performance in a proficiency testing programme or on the basis of other criteria of merit.     

International Association of Geoanalysts' Protocol for the Certification of Geological and Environmental Reference Materials: A Supplement

The International Association of Geoanalysts (IAG) published a protocol for the certification of reference materials in close accord with the International Organisation for Standardisation (ISO) guidelines (Kane et al. 2003). This article supplements that protocol, providing additional discussion of best approaches for pre-selecting laboratories for participation in certification projects. This discussion also makes a distinction between inter-laboratory certifications, where n = 15 is the general standard, and expert laboratory certifications, where a much smaller number of laboratories will be deemed qualified to provide data of the quality needed for certification.     

A Review of the IAG GeoPT™ and Certification Programmes,their Protocols,and the Differences between the Original and Potential Modifications to the Certification Protocol

The IAG conducts two programmes, the GeoPT ^? proficiency test and a certification programme that are closely interconnected. Both support the quality control/quality assurance activities of geochemical laboratories. Each derives an estimate of ‘true value’ for a number of samples, but arrives at that estimate, and its uncertainty, differently. This review discusses the history of the two programmes and compares the ‘true values’ and their uncertainties obtained through each. It then considers ‘fitness‐for‐purpose’ issues related to both GeoPT ^? and certification uncertainties. Issues related to potential modification of the IAG protocol for certification are also considered.     

Developments at ISO/REMCO and its Impact on the Production and Use of Geological Reference Materials

During the past decade the work of ISO/REMCO, the International Organization for Standardization’s Technical Committee on Reference Materials, was dedicated to achieving global harmonisation, and true involvement of the member countries. The first major accomplishment was the clarification of the terminology in the definitions for reference material and certified reference material, which were published as an amendment to ISO Guide 30 in 2008. The next milestone was the recognition that ISO Guide 34 (‘General requirements for the competence of reference material producers’) be used in conjunction with ISO/IEC 17025 for the accreditation of reference material producers. The third edition of ISO Guide 34 published in November 2009, clarifies the acceptable procedures for the certification of reference materials. This paper will discuss the role of ISO/REMCO in formalising the procedures for the accreditation of reference material producers and the evolution of the terms reference material and certified reference material. The paper will conclude with a case study, where a primary method in a single laboratory – one of the recognised acceptable metrologically valid procedures according to ISO Guide 34 – was used for the certification of reference materials. The reference materials are South African Reference Material SARM 2 (Syenite), SARM 3 (Lujavrite) and SARM 4 (Norite) from the suite of six NIMROCs that were originally certified by the Council for Mineral Technology (MINTEK) in South Africa in the 1970s.     

GeoPT4. An International Proficiency Test for Analytical Geochemistry Laboratories - Report on Round 4 (March 1999)

Results are presented from the seventy five laboratories participating in GeoPT4, round four of the international proficiency testing programme for analytical geochemistry laboratories. Laboratories were required to analyse the sample OU-2 (Belford dolerite) using routine methods of analysis. The sample was distributed during September 1998 with a deadline for the submission of results of 15th January 1999. In this report, contributed data are analysed and z-scores calculated. Z-score values provide participating laboratories with information concerning the quality of their results and indicate data that may be subject to unsuspected analytical bias. Laboratories are invited to examine these data and take the appropriate action.     

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。     

THE PREPARATION AND CERTIFICATION OF FOURTEEN SOUTH AFRICAN SILICATE ROCKS FOR USE AS REFERENCE MATERIALS*

This report describes the preparation, analysis and certification of South African Reference Materials (SARMs) 39 to 52. These materials, which comprise a suite of rock materials originally named SAROCs, were collected from many locations within the Republic of South Africa. Nineteen laboratories in five countries used a variety of analytical techniques to provide the analytical results. The certified and tentative values that have been assigned to a number of constituents are presented in tabular form in appendices.     

Determination of Platinum‐Group Elements in OPY‐1: Comparison of Results using Different Digestion Techniques

A new proficiency testing sample, OPY‐1 (ultramafic rock), the basis of the twentieth international proficiency test of analytical geochemistry laboratories (GeoPT 20), was recently prepared by the International Association of Geoanalysts (IAG). This paper reports analytical data for Os, Ir, Ru, Rh, Pt and Pd with different digestion techniques, including an improved Carius tube, Carius tube combined with HF dissolution and alkaline fusion. About 4–15% of the PGEs are in the silicate phase, which cannot be leached by aqua regia even when digested at 300 °C with the Carius tube technique. Both the Carius tube technique combined with HF dissolution and alkaline fusion can obtain reliable data. The results demonstrated that OPY‐1 is sufficiently homogeneous at a 2 g test portion level to be suitable as a reference material for method validation. The procedure for sealing the Carius tube was simplified and the recommended digestion procedures are provided.     

Preparation of Four Chromium Ore Reference Materials

The preparation and characterisation of four chromium ore reference materials are described in this paper. The sample material for GCr‐1, GCr‐3 and GCr‐4 was collected from chromite deposits in Tibet, Qinghai province and Inner Mongolia. GCr‐2 is a composite sample from GCr‐1 and GCr‐4. Sample homogeneity was tested by WD‐XRF and the relative standard deviations were < 1.0%. An F‐test showed that all four materials were homogeneous. Thirteen laboratories involved in the inter‐laboratory programme provided 672 determinations (eighteen oxides and elements). Sixteen components were characterised as certified values, of which Cr₂O₃ ranged from 17.59 to 57.80% m/m. The contents of FeO and CO₂ were taken as reference values.     

中国地质标准物质制备技术与方法研究进展

评介了中国地质标准物质研制中技术方法方面的研究进展,包括样品加工技术,粒度检测与表征方法,均匀性检验与评价,最小取样量的确定,稳定性检验及其结果表述,定值方式,分析方法、数据处理及定值条件,不确定度评价与量值溯源保证等。对照国家相关的技术规范、国际标准化组织(ISO)的相关指南和国际地质分析者协会(IAG)关于地质标准物质研制的协议,讨论了目前中国地质标准物质制备技术的现状及未来的发展。     

The Reliability of Assigned Values from the GeoPT Proficiency Testing Programme from an Evaluation of Data for Six Test Materials that have been Characterised as Certified Reference Materials

Assigned values derived from the GeoPT proficiency testing programme were compared with certified values for six certified reference materials that have been used as test materials in the GeoPT programme. Statistical analysis showed that there were few significant differences between these sets of data and that these differences had no significant impact on the GeoPT assessment when fitness‐for‐purpose criteria were taken into account.     

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。     

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。