Measurement uncertainty and the use of reference materials

The use of (certified) reference materials and quality control materials can form a suitable basis for evaluating measurement uncertainty of routine measurements. In particular when these materials are used for quality control purposes, it is not always evident how the quality control data can be used in the uncertainty budget of a routine measurement. Current guidance documents on the evaluation of measurement uncertainty and the use of reference materials treat this subject only in part, or in very generic terms. ISO/REMCO has established a new working group that will provide practical guidance and examples on how to use quality control data in the evaluation of measurement uncertainty. A short introduction to the subject is given.

Some aspects of the evaluation of measurement uncertainty using reference materials

To ensure and to confirm the required traceability according to the definition given in the International Vocabulary of Basic and Standard Terms in Metrology, three main aspects need to be considered in practice: "stated reference", "unbroken chain of calibration" and "stated uncertainty". For a certain spectrochemical result, each of the aspects above mentioned is highly dependent on measurement uncertainty, both on its magnitude and how it was estimated. The paper describes the experience of the Romanian National Institute of Metrology (INM) in estimating measurement uncertainty during certification of reference materials, in metrological calibration and during specific analytical processes. Practical examples of the use of reference materials or certified reference materials issued by the INM to estimate measurement uncertainty are discussed for their applicability in spectrochemical and turbidity analysis. Some aspects of the use of analysis of variance (ANOVA) to obtain additional information on the components of measurement uncertainty and to identify the magnitude of individual random effects are presented.     

Some aspects of the evaluation of measurement uncertainty using reference materials

To ensure and to confirm the required traceability according to the definition given in the International Vocabulary of Basic and Standard Terms in Metrology, three main aspects need to be considered in practice: “stated reference”, “unbroken chain of calibration” and “stated uncertainty”. For a certain spectrochemical result, each of the aspects above mentioned is highly dependent on measurement uncertainty, both on its magnitude and how it was estimated. The paper describes the experience of the Romanian National Institute of Metrology (INM) in estimating measurement uncertainty during certification of reference materials, in metrological calibration and during specific analytical processes. Practical examples of the use of reference materials or certified reference materials issued by the INM to estimate measurement uncertainty are discussed for their applicability in spectrochemical and turbidity analysis. Some aspects of the use of analysis of variance (ANOVA) to obtain additional information on the components of measurement uncertainty and to identify the magnitude of individual random effects are presented.     

Some aspects of the evaluation of measurement uncertainty using reference materials

 In practice there are three aspects that need to be considered in order to achieve the required traceability according to its definition: the 'stated reference', the 'unbroken chain of calibrations' and the "stated uncertainty". For a certain chemical result, each of these aspects highly depends on the measurement uncertainty, both on its magnitude and how it was estimated. Therefore, the paper describes the experience of the Romanian National Institute of Metrology in estimating measurement uncertainty during the certification of reference materials (RMs), in metrological activities (calibration, pattern approval, periodical verification, etc.), as well as during the analytical measurement process. Practical examples of estimation of measurement uncertainty using RMs or certified reference materials are discussed for their applicability in spectrophotometric and turbidimetric analysis. Use of the analysis of variance to obtain some additional information on the components of measurement uncertainty and to identify the magnitude of individual random effects is described. Received: 12 November 1999 / Accepted: 25 February 2000     

The use of reference materials in the finnish industry

Summary A report is given on the results of a survey of the use of reference materials in the chemical industry of Finland. It has been found that there is virtually no production of reference materials in Finland and that most of the materials used are not certified. Mostly, different materials are used which are pharmacopoeia standards with regard to their physical properties. Some companies were found to use more than 100 different reference materials.

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Verwendung von Referenzmaterialien in Finnland

Zusammenfassung Es wird über das Ergebnis einer Umfrage zur Benutzung von Referenzmaterialien in der chemischen Industrie Finnlands berichtet. Es ergab sich, daß in Finnland praktisch keine solchen Substanzen hergestellt werden und die meisten der verwendeten Materialien nicht zertifiziert sind. Meist werden verschiedenartige chemische Substanzen verwendet, die in Bezug auf ihre physikalischen Eigenschaften einem Arzneibuchstandard entsprechen. Einige Firmen benutzen mehr als 100 verschiedene Referenzmaterialien.

Presented at Euroanalysis III conference, Dublin, August 20–25, 1978     

The use of reference materials in the fossil fuels quality control

The determination of trace elements in fossil fuels is of primary importance to achieve correct evaluation of environmental impact of power plants. The characterization of coals and fuel oils can be carried out by several analytical techniques such as ICP-MS, FI-HG-AAS, ETA-AAS, ICP-AES and XRF. The accuracy of the analysis, done to routine basis, can be systematically checked by means of the reference materials available or comparing the results obtained by different techniques. Quality control activities in the field of trace element determination in fossil fuels (coal and fuel oil) are described. The determination of As, Hg and Se in coals was carried out by different techniques (NAA, FI-HG-AAS and FI-ICP-MS) together with the determination of several trace metals in residual fuel oils by NAA, ETA-AAS and ICP-MS. The use of certified reference materials in order to check the accuracy of procedures is discussed and the results obtained for NIST 1632a and NIST 1632b (coal samples) and NIST 1634b and NIST 1619 (fuel oil samples) are reported.     

The use of certified reference materials in the Romanian traceability scheme

 For ensuring the traceability and uniformity of measurement results, the main objectives of national metrology programmes in chemistry are to calibrate and verify measuring instruments, to evaluate the uncertainty of measurement results and to intercompare the analytical results, etc. The concept of traceability has developed recently in chemical measurements, thus, an attempt to implement the principles of metrological traceability especially by appropriateness calibration using composition certified reference materials (CRMs) is underlined. Interlaboratory comparisons are also a useful response to the need for comparable results. The paper presents some aspects and practices in the field of spectrometric measurement regarding the metrological quality of the traceability by calibrating the instruments using suitable and reliable CRMs. The uncertainty of results, as a measure of the reliability that can be placed on them, has been adequately described in different documents and, as a consequence, some examples of evaluating the measurement uncertainty are described. The relationship between uncertainty and traceability, as two fundamental concepts of metrology which are intimately linked, is underlined. Received: 12 November 1999 / Accepted: 10 December 1999     

Ion-implanted reference standards for use in microchemical analysis of materials

Summary A concise overview has been given of the present state of development of ion-implanted reference standards for the calibration of instrumental methods of microchemical characterization of solid materials.

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Ionen-implantierte Standardpräparate für die Mikroanalyse

Zusammenfassung Der gegenwärtige Entwicklungsstand ionenimplantierter Standardpräparate für die Eichung instrumenteller Mikromethoden der chemischen Feststoffanalyse wurde besprochen.

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Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980.     

The use of laboratory prepared reference materials in nutrient analysis

Summary The need for laboratory prepared reference materials is discussed as are experiences gained during five years of their use in the analysis of foods for trace nutrients. Ways of monitoring results are described and the possibility of providing certified reference materials for some of the B group vitamins in foods is examined.     

Availability of reference materials: COMAR the database for certified reference materials

COMAR is the international database for certified reference materials. A new user-friendly web-based version, COMAR², has been developed by BAM and CONET Consulting AG which will be available in December 2002. The advantages of COMAR² are briefly explained.Presented at the International ILAC/IAF Conference on Accreditation in Global Trade, 23-25 September 2002, Berlin, Germany     

The interpretation and use of stability data in the certification of reference materials

 Stability tests are carried out on candidate reference materials in order to ascertain that the certification values continue to be valid a reasonable time after completion of the certification analysis. These tests are also used for recommending storage conditions, as well as the duration of storage before certification values need be rechecked. BCR (Community Bureau of Reference) reference materials do not normally have an expiry date, but rely on stability monitoring throughout the lifetime of the certified material. The 1997 version of the BCR Guidelines for the production and certification of reference materials does, however, take into account the necessity of limiting the validity of a certification, when degradation of the material during storage cannot be ignored. This paper discusses an example of significant degradation taking place between the time of completion of the certification analysis and the issue of a formal certificate. Various options are presented together with an account of their influence on the certified values and their uncertainties. Received: 3 October 1997 · Accepted: 3 November 1997     

The use of certified reference materials in the verification of analytical data and methods

An experimental design is proposed for the verification of the accuracy and precision of an analytical method by its application to certified reference materials.     

On the use of reference materials in gamma-ray spectrometric efficiency calibration for environmental samples

In order to calibrate a gamma-ray spectrometer for radioactivity measurements in environmental samples, it is essential to use standard radioactive sources in the appropriate geometrical configuration. However, the lack of standard sample due to any reason would necessitate the use of reference materials as reliable alternative. They often appear in many matrices and densities. Accordingly, special attention should be drawn towards optimizing the calibration. This work studies the errors encountered because of the attenuation process due to the density difference of the samples (including reference samples) aliquots with identical matrix contents. The highest effect was noticed in the lower energy regions. This study suggests that even for the reference samples with the same matrix, it is necessary to set a recommended density for the measurement process to avoid the errors due to the attenuation. If this is not practically possible it is recommended that attenuation correction due to matrix contents followed by another correction due to density correction would be a reliable approach to reach an optimum calibrating condition.     

Development and use of reference materials in India – status and plans

Reference materials development activities in India started during the period 1955–1960 for quality control in the production and use of drugs and pharmaceuticals. While the practice of import and distribution gradually accelerated in some areas, including medical, environment etc., the earliest known development of Certified Reference Materials (CRMs) within the country began with the preparation of metallurgical CRMs somewhere around 1965. A few more area-specific programs involving preparation of CRMs for quality control in the electronic industries, food and food products etc., began in the past decade. A common national program covering these activities was initiated in 1996, through organization of a national workshop on the subject and formation of a National Task Force for the development and use of reference materials in the country. The existing status and the priority needs of reference materials have been compiled by the Task Force, and a program has also been prepared for development of some of the urgently required CRMs within the country.

     

The deplorable state of the description of the use of certified reference materials in the literature

A detailed survey of 26 scientific journals showed that journal editors and a majority of authors of the reviewed papers seem unconcerned by the importance of correctly reporting their use of certified reference materials (CRMs). Only around 55% of the abstracts surveyed mention the use of CRMs described in these papers. This, however, is of key importance as the abstract of a paper is most widely available in electronic media. Many authors mentioned the use of CRMs in passing, often in incomplete form and without giving any details of the results obtained. Some are confused about the source of the reference material used, as they fail to report the type or the producer of CRMs applied. Others use materials that do not match the samples analyzed or do not see the need to use any CRM, despite the availability of suitable materials. Even in cases where correct data were given for type and producer of the CRMs, frequently the proper use and statistical evaluation are questionable. To improve this situation it is necessary that publishers should give recommendations where and how the use of CRMs should be described.     

About the adequacy of reference materials

Summary Any analytical procedure includes at least six steps: (1) the sampling; (2) the conditioning of the sample after sampling and its transport to the analytical laboratory; (3) the treatment of the sample at the laboratory; (4) the introduction of the sample into the measurement system; (5) the measurement itself; (6) the processing of the analytical signal and its results. We propose to measure the adequacy of an RM by the factor =^x/^RM, where ^x and ^RM are the errors associated with the analysis of a sample (x) and the RM, respectively. A factor _i can be defined for each step i of the analytical process. The paper examines the means of estimating the parameters _i ^x , _i ^RM and _i for each step of the analytical process. All _i ^x terms excluding those related to the sample treatment and to the measurement can be measured without the use of an RM. To determine the error to be expected from the sample preparation and the measurement it is sufficient to use am RM which is taylored to these two steps only, rather than to the entire analytical process. This may be done for example by spiking a sample with an RM providing the necessary analytical signal. Such RMs are simple and inexpensive to prepare and have very broad applications.