The Use of Reference Materials: A Tutorial

Any review of the analytical literature shows that, while reference materials are routinely used in laboratories world-wide, not all uses follow ISO Guide 33 (1989), which outlines best practices. Analytical data quality can suffer as a result. This paper reviews the various uses that the geoanalytical community has made of reference materials from a historical perspective, and suggests improvements in practice that would more closely follow ISO Guide 33 recommendations.     

Determination of Molybdenum, Antimony and Tungsten at sub μg g−1 Levels in Geological Materials by ID-FI-ICP-MS

We have developed a rapid and accurate method for the determination of Mo, Sb and W in geological samples using isotope dilution inductively coupled plasma-mass spectrometry with a flow injection system (ID-FI-ICP-MS). The chemical procedure requires HF digestion of the sample with a Mo-Sb-W mixed spike, subsequent evaporation and dissolution of Mo, Sb and W from Mg and Ca fluorides with HF. Recovery yields of Mo, Sb and W in the extraction were > 94% for samples of peridotite, basalt and andesite composition, with the exception of W in samples of peridotite composition for which recovery was 81%. No matrix effects were observed in the determination of the isotope ratios of Mo, Sb and W in solutions prepared from peridotite, basalt and andesite samples down to a dilution factor of 100. Detection limits of Mo, Sb and W in silicate materials were at the several ng g⁻¹ level. Analysis of the silicate reference materials PCC-1, DTS-1, BCR-1, BHVO-1, AGV-1 from the US Geological Survey and JP-1, JB-1, -2, -3, JA-1, -2, and -3 from the Geological Survey of Japan as well as the Smithsonian reference Allende powder yielded reliable Mo, Sb and W concentrations. The repeatability in the analysis of basalts and andesites was < 9%. This technique requires only 0.2 ml sample solution, and is therefore suitable for analyzing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates.     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

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.     

Determination of Zr and Hf in a Flux-Free Fusion of Whole Rock Samples using Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) with Isotope Dilution Calibration

Isotope dilution calibration has been applied to the determination of Zr and Hf in whole rocks by laser ablation (LA)-ICP-MS. Enriched isotopes were added during the preparation of flux-free, synthetic whole rock glasses and homogenised through a combination of grinding and fusion. This method avoids problems, such as solution instability and the chemical resistance of minerals such as zircon, inherent in acid digestion sample preparation. The use of isotope dilution removes the need for external calibration using certified reference material glasses such as NIST SRM 612 for which certified Zr and Hf values are not available. The precision of Zr and Hf determinations were found to be < 1% and 3.5% respectively, limited by Poisson counting statistics which contributed to 50% of the final precision of analysis. Measured values correlate closely with compiled literature values.     

Producing Certified Reference Materials at the Central Geological Laboratory of Mongolia

This paper briefly outlines the production and certification of reference materials at the Central Geological Laboratory (CGL) of Mongolia. The marketing of CRMs produced in Mongolia, as well as problems encountered in internationally recognised certification attempts and some proposed solutions, are discussed. The basic elements of the CGL’s strategy for the development of the CRM sector are to produce high quality CRMs according to the requirements of internationally recognised norms, to consider the market needs, to certify the RMs at the international level and to widely advertise them to the geochemical community. The CGL has already established the basis for the further development of this sector by, for instance, accreditation under ISO/IEC 17025, by modernising its preparation technology, by cooperation with international organisations in the field of CRMs and by permanent participation in the International Association of Geoanalysts’ GeoPT™ proficiency testing programme.     

Reference Values Following ISO Guidelines for Frequently Requested Rock Reference Materials

We present new reference values for nineteen USGS, GSJ and GIT‐IWG rock reference materials that belong to the most accessed samples of the GeoReM database. The determination of the reference values and their uncertainties at the 95% confidence level follows as closely as possible ISO guidelines and the Certification Protocol of the International Association of Geoanalysts. We used analytical data obtained by the state‐of‐the‐art techniques published mainly in the last 20 years and available in GeoReM. The data are grouped into four categories of different levels of metrological confidence, starting with isotope dilution mass spectrometry as a primary method. Data quality was checked by careful investigation of analytical procedures and by the application of the Horwitz function. As a result, we assign a new and more reliable set of reference values and respective uncertainties for major, minor and a large group of trace elements of the nineteen investigated rock reference materials.     

Iron Isotopic Compositions of Geological Reference Materials and Chondrites

High‐precision iron isotopic compositions for Fe‐bearing geological reference materials and chondrites with a wide range of matrices (e.g., silicates, oxides, organic‐bearing materials) are reported. This comprehensive data set should serve as a reference for iron isotopic studies across a range of geological and biological disciplines for both quality assurance and inter‐laboratory calibration. Where comparison is available, the iron isotopic compositions of most geological reference materials measured in this study were in agreement with previously published data within quoted uncertainties. Recommendations for the reporting of future iron isotopic data and associated uncertainties are also presented. Long‐term repeat analyses of all samples indicate that highly reproducible iron isotopic measurements are now obtainable (± 0.03‰ and ± 0.05‰ for δ⁵⁶Fe and δ⁵⁷Fe, respectively).     

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).     

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.     

How Fit Are Your Data?

Most laboratories aim to produce data of the highest quality. Trying to lower uncertainties to infinitesimal figures and push detection limits even lower are valid goals. However, is it possible to overachieve? Are old data still of good enough quality to be usable? In a geochemical context, the main goal of producing analytical results is to answer geological or environmental questions. Not all scientific problems require the same data quality. What is really required are data of adequate quality – i.e., ‘fit-for-purpose’– to ensure that the geological problem at hand can be solved. Furthermore, it is doubtful that uncertainties and reproducibilities associated with field sampling are better than those from laboratories. It is thus proposed that, as geoanalysts, we encourage data users (students, colleagues or referees) to ensure that their analytical results are of sufficient quality to solve the problem. However, authors have to demonstrate, through the use of reproducibility testing, reference and quality control materials, that the quality of their results is sufficient to solve the problem. Uncertainties and detection limits in publications should not only be evaluated with respect to a set value, such as 10%, but also with regard to the geological problem to be solved.     

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.     

Production and Certification of a Unique Set of Isotope and Delta Reference Materials for Boron Isotope Determination in Geochemical,Environmental and Industrial Materials

Isotopic reference materials are essential to enable reliable and comparable isotope data. In the case of boron only a very limited number of such materials is available, thus preventing adequate quality control of measurement results and validation of analytical procedures. To address this situation a unique set of two boron isotope reference materials (ERM‐AE102a and ‐AE104a) and three offset δ¹¹B reference materials (ERM‐AE120, ‐AE121 and ‐AE122) were produced and certified. The present article describes the production and certification procedure in detail. The isotopic composition of all the materials was adjusted by mixing boron parent solutions enriched in ¹⁰B or ¹¹B with a boron parent solution having a natural isotopic composition under full gravimetric control. All parent solutions were analysed for their boron concentration as well as their boron isotopic composition by thermal ionisation mass spectrometry (TIMS) using isotope dilution as the calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agreed very well with the isotopic composition obtained from different TIMS techniques. Stability and homogeneity studies that were performed showed no significant influence on the isotopic composition or on the related uncertainties. The three reference materials ERM‐AE120, ERM‐AE121 and ERM‐AE122 are the first reference materials with natural δ¹¹B values not equal to 0‰. The certified δ¹¹B values are ?20.2‰ for ERM‐AE120, 19.9‰ for ERM‐AE121 and 39.7‰ for ERM‐AE122, each with an expanded uncertainty (k = 2) of 0.6‰. These materials were produced to cover about three‐quarters of the known natural boron isotope variation. The ¹⁰B enriched isotope reference materials ERM‐AE102a and ERM‐AE104a were produced for industrial applications utilising ¹⁰B for neutron shielding purposes. The certified ¹⁰B isotope abundances are 0.29995 for ERM‐AE102a and 0.31488 for ERM‐AE104a with expanded uncertainties (k = 2) of 0.00027 and 0.00028, respectively. Together with the formerly certified ERM‐AE101 and ERM‐AE103 a unique set of four isotope reference materials and three offset δ¹¹B reference materials for boron isotope determination are now available from European Reference Materials.     

Determination of Total Sulfur in Fifteen Geological Materials Using Inductively Coupled Plasma‐Optical Emission Spectrometry (ICP‐OES) and Combustion/Infrared Spectrometry

A method for the determination of total sulfur in geological materials by inductively coupled plasma‐optical emission spectrometry (ICP‐OES) is described. We show that good results were obtained using this method even for sample types with very low (< 20 μg g^?1) sulfur concentration (e.g., peridotite). Sulfur was determined in fifteen geological reference materials with different sulfur contents. For reference materials with certified sulfur contents, the ICP‐OES method gave results in excellent agreement with certified values, and uncertainties better than 4% RSD. ICP‐OES results for sulfur in other reference materials yielded RSDs better than 10%, where S concentrations were > 100 μg g^?1 (except for diabase W‐2a, 16% RSD). Reference materials with lower sulfur contents (< 40 μg g^?1) showed much higher RSDs (17–18%). Except for RMs with certified values for sulfur, most data obtained by the combustion infrared detection method generally showed higher concentrations than those measured by ICP‐OES and a better RSD (≤ 8% for all materials except DTS‐2b).     

Accurate and Precise Elemental Abundance of Zinc in Reference Materials by an Isotope Dilution Mass Spectrometry TIMS Technique

A thermal ionisation mass spectrometric technique enabled the abundance of Zn in geological and biological reference materials and water samples to be measured by double spiking isotope dilution mass spectrometry enriched in the ⁶⁷Zn and ⁷⁰Zn isotopes. In the past, thermal ionisation mass spectrometry proved to be difficult for low-level zinc isotopic measurements. The size of Zn samples used for isotopic determination, in particular the biological RMs, represents an important breakthrough. These results represent the most accurate and precise concentrations measured for Zn in these samples. The maximum fractional uncertainty was that for TILL-3 (2%), while the minimum fractional uncertainty was 0.7% for both BCR-1 and W-2. The inhomogeneity of Zn in HISS-1 was revealed while other reference materials appeared homogeneous at the 95% confidence uncertainty. The certified concentration of Zn in HISS-1 and IMEP-19 by their producers are 28% and 3.8% higher than the values measured in this work. These are the first Zn concentration measurements in these materials by the isotope dilution-TIMS technique, except for BCR-1, NIES N^o 9 and IMEP-19. Reducing the blank enabled accurate measurement in water at the ng g^-1 level demonstrating the applicability of the technique for low-level Zn samples.     

New Chinese National Reference Materials for Hydrogen and Oxygen Isotopes in Water

The Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences recently prepared four certified reference materials for hydrogen and oxygen stable isotopes in water, which are called ‘China Standard Water' (CSW)‐HO1–HO4 (hereafter referred to as HO1–HO4). These reference materials are intended for calibration purposes and provide reference values of their relative difference in ²H/¹H and ¹⁸O/¹⁶O isotope‐amount ratios expressed in delta notation, normalised to the VSMOW–SLAP scale. The certified values of the reference materials were determined by an interlaboratory comparison of results from eleven participating laboratories. This paper describes in detail the production and certification procedure of the four reference materials. The first analytical data for the reference materials are also provided using a variety of analytical techniques, namely CO₂–H₂O equilibration and laser spectroscopy for δ¹⁸O and Cr reduction, as well as H₂–H₂O equilibration, laser spectroscopy, and high‐temperature conversion for δ²H. The reference values for materials HO1–HO4 and their associated uncertainties are assigned.     

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.     

Calibration of the New Certified Reference Materials ERM‐AE633 and ERM‐AE647 for Copper and IRMM‐3702 for Zinc Isotope Amount Ratio Determinations

The commonly used, but no longer available, reference materials NIST SRM 976 (Cu) and ‘JMC Lyon’ (Zn) were calibrated against the new reference materials ERM^®‐AE633, ERM^®‐AE647 (Cu) and IRMM‐3702 (Zn), certified for isotope amount ratios. This cross‐calibration of new with old reference materials provides a continuous and reliable comparability of already published with future Cu and Zn isotope data. The Cu isotope amount ratio of NIST SRM 976 yielded δ^65/63Cu values of ?0.01 ± 0.05‰ and ?0.21 ± 0.05‰ relative to ERM^®‐AE633 and ERM^®‐AE647, respectively, and a δ^66/64Zn_IRMM‐3702 value of ?0.29 ± 0.05‰ was determined for ‘JMC Lyon’. Furthermore, we separated Cu and Zn from five geological reference materials (BCR‐2, BHVO‐2, BIR‐1, AGV‐1 and G‐2) using a two‐step ion‐exchange chromatographic procedure. Possible isotope fractionation of Cu during chromatographic purification and introduction of resin‐ and/or matrix‐induced interferences were assessed by enriched ⁶⁵Cu isotope addition. Instrumental mass bias correction for the isotope ratio determinations by MC‐ICP‐MS was performed using calibrator‐sample bracketing with internal Ni doping for Cu and a double spike approach for Zn. Our results for the five geological reference materials were in very good agreement with literature data, confirming the accuracy and applicability of our analytical protocol.     

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.     

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.