Reference materials and certified reference materials for spectrometry in Romania

Several reference materials (RMs) and certified reference materials (CRMs) are widely used in Romania as measurement standards in different spectrochemical measurements. Among them, single element standard solution certified for their mass concentration play a key role in ensuring the required traceability of results expressed in this measurement unit. A short review of the locally available elemental RMs and CRMs used in atomic spectrometry or in other analytical techniques where aqueous standard solutions are required (usually called RMs or CRMs for spectrometry) is given. The experience of the INM in preparation and certification of such materials is described. Some aspects regarding their use for ensuring the accuracy and for confirmation of the traceability of analytical measurements, especially through calibration and metrological validation of main instrument performances, are discussed.     

Guidance on the contents of accompanying documentation for reference materials (RMs)

The use of reference materials (RMs) is a key activity for the improvement and maintenance of a worldwide coherent measurement system. As detailed in ISO Guide 33, RMs with different characteristics are used in measurement processes, for the purpose of precision control, bias assessment, calibration, assigning values to other materials, and maintaining conventional scales, to name a few. For the establishment of metrological traceability of measurement results to international scales or other measurement standards, proper use of certified reference materials (CRMs) is essential. From the perspective of a reference material producer, the documentation that is provided with an RM is the value-adding component of the material; for the user, the document is critical for the correct implementation and use of the RM in the measurement process. The ISO Committee on Reference Materials (ISO/REMCO) recognised the importance of the documentation that accompanies a reference material as early as 1981 when the first edition of ISO Guide 31 was published. The third edition of the Guide that was published recently considers the appropriate accompanying documentation for all types of reference materials, i.e. CRMs and non-certified RMs.     

New developments in the production and use of CRMs in Romania

 A lot of effort is being made in Romania to meet the present main strategic goal – EU integration. Since the confidence in measurements is of considerable importance in almost every field of activity, the National Institute of Metrology (INM) is involved in improving its calibration and measurement capabilities to provide services in accordance with the latest European Regulation. Within this framework the assurance of the required traceability of all measurements plays a most important role. As reliable analytical measurements depend largely upon reference materials and the assurance of the traceability of amount measurements is still developing in Romania, a new approach regarding the function of Certified Reference Materials (CRMs) may be emphasized. The experience of the INM as well as new developments in Romania in preparation and certification of Reference Materials (RMs) are described. A short review of the locally available RMs and CRMs is given. Some aspects regarding the use of RMs and CRMs, especially for calibration, are discussed for their applicability for analytical measurements. Received: 31 October 2002 Accepted: 24 January 2003 Presented at CERMM-3, Central European Reference Materials and Measurements Conference: The function of reference materials in the measurement process, May 30–June 1, 2002, Rogaška Slatina, Slovenia Correspondence to M. Buzoianu     

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     

Correcting measurement errors using reference materials in method validation

Quality assurance and method validation are needed to reduce false decisions due to measurement errors. In this context accuracy and standard uncertainty for the analytical method need to be considered to ensure that the performance characteristics of the method are understood. Therefore, analytical methods ought to be validated before implementation and controlled on a regular basis during usage. For this purpose reference materials (RMs) are useful to determine the performance characteristics of methods under development. These performance parameters may be documented in the light of a method evaluation study and the documentation related to international standards and guidelines. In a method evaluation study of Pb in blood using reference samples from the Laboratoire Toxicologie du Quèbec, Canada, a difference between the systematic errors was observed using a Perkin-Elmer Model 5100 atomic absorption spectrometer and a Perkin-Elmer Model 4100 atomic absorption spectrometer, both with Zeeman background correction. For measurement of blood samples, the performance parameters obtained in the method evaluation studies, i.e. slopes and intercepts of the method evaluation function (MEF), were intended to be used for correcting the systematic errors. However, the number of MEF samples was insufficient to produce an acceptable SD for the MEF slopes to be used for correction. In a method evaluation study on valproate in plasma using the SYVA's EMIT assay on COBAS MIRA S a significant systematic error above the concentration 300 mmol dm^–3 was demonstrated (slope 0.9541) and consequently the slope was used for correction of results. For analytes, where certified RMs (CRMs) exist, a systematic error of measurements can be reduced by correcting errors by assessment of the trueness as recommended in international guidelines issued by ISO or the National Institute of Standards and Technology (NIST). When possible, the analysis of several RMs, covering the concentration range of interest, is the most useful way to investigate measurement bias. Unfortunately, until recently only few RMs existed and only few had been produced and certified by specialized organizations such as NIST or the Standards, Measurements and Testing (SMT, previously BCR) programme. Due to the lack of such RMs, network organizations are nowadays established with the aim of supporting the correct use and production of high-quality CRMs.     

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     

Lifetime of the traceability chain in chemical measurement

Since the uncertainty of each link in the traceability chain (measuring analytical instrument, reference material or other measurement standard) changes over the course of time, the chain lifetime is limited. The lifetime in chemical analysis is dependent on the calibration intervals of the measuring equipment and the shelf-life of the certified reference materials (CRMs) used for the calibration of the equipment. It is shown that the ordinary least squares technique, used for treatment of the calibration data, is correct only when uncertainties in the certified values of the measurement standards or CRMs are negligible. If these uncertainties increase (for example, close to the end of the calibration interval or shelf-life), they are able to influence significantly the calibration and measurement results. In such cases regression analysis of the calibration data should take into account that not only the response values are subjects to errors, but also the certified values. As an end-point criterion of the traceability chain destruction, the requirement that the uncertainty of a measurement standard should be a source of less then one-third of the uncertainty in the measurement result is applicable. An example from analytical practice based on the data of interlaboratory comparisons of ethanol determination in beer is discussed. Received: 5 October 2000 Accepted: 3 December 2000     

Using inductively coupled plasma-mass spectrometry for calibration transfer between environmental CRMs

Multielement analyses of environmental reference materials have been performed using existing certified reference materials (CRMs) as calibration standards for inductively coupled plasma-mass spectrometry. The analyses have been performed using a high-performance methodology that results in comparison measurement uncertainties that are significantly less than the uncertainties of the certified values of the calibration CRM. Consequently, the determined values have uncertainties that are very nearly equivalent to the uncertainties of the calibration CRM. Several uses of this calibration transfer are proposed, including, re-certification measurements of replacement CRMs, establishing traceability of one CRM to another, and demonstrating the equivalence of two CRMs. RM 8704, a river sediment, was analyzed using SRM 2704, Buffalo River Sediment, as the calibration standard. SRM 1632c, Trace Elements in Bituminous Coal, which is a replacement for SRM 1632b, was analyzed using SRM 1632b as the standard. SRM 1635, Trace Elements in Subbituminous Coal, was also analyzed using SRM 1632b as the standard.     

Using inductively coupled plasma–mass spectrometry for calibration transfer between environmental CRMs

Multielement analyses of environmental reference materials have been performed using existing certified reference materials (CRMs) as calibration standards for inductively coupled plasma–mass spectrometry. The analyses have been performed using a high-performance methodology that results in comparison measurement uncertainties that are significantly less than the uncertainties of the certified values of the calibration CRM. Consequently, the determined values have uncertainties that are very nearly equivalent to the uncertainties of the calibration CRM. Several uses of this calibration transfer are proposed, including, re-certification measurements of replacement CRMs, establishing traceability of one CRM to another, and demonstrating the equivalence of two CRMs. RM 8704, a river sediment, was analyzed using SRM 2704, Buffalo River Sediment, as the calibration standard. SRM 1632c, Trace Elements in Bituminous Coal, which is a replacement for SRM 1632b, was analyzed using SRM 1632b as the standard. SRM 1635, Trace Elements in Subbituminous Coal, was also analyzed using SRM 1632b as the standard.     

Certified reference materials for inorganic and organic contaminants in environmental matrices

Chemical measurements often constitute the basis for informed decision-making at different levels in society; sound decision-making is possible only if the quality of the data used is uncompromised. To guarantee the reliability and comparability of analytical data an intricate system of quality-assurance measures has to be put into effect in a laboratory. Reference materials and, in particular, certified reference materials (CRMs) are essential for achieving traceability and comparability of measurement results between laboratories and over time. As in any other domain of analytical chemistry, techniques used to monitor the levels and fate of contaminants in the environment must be calibrated using appropriate calibration materials, and the methods must be properly validated using fit-for-purpose matrix-matched CRMs, to ensure confidence in the data produced. A sufficiently large number of matrix CRMs are available for analysis of most elements, and the group of chemicals known as persistent organic pollutants, in environmental compartments and biota. The wide variety of analyte/level/matrix/matrix property combinations available from several suppliers enables analysts to select CRMs which sufficiently match the properties of the samples they analyse routinely. Materials value-assigned for the so-called emerging pollutants are scarce at the moment, though an objective of current development programmes of CRM suppliers is to overcome this problem.     

Certified reference materials for the quality control of environmental analysis within the standards,measurements and testing programme (formerly BCR)

A great number of analyses is performed every year, the results of which are used for many purposes, e.g. the quality of goods and food, the status of quality of the environment or the health of patients. The accuracy of these results is a prerequisite for a good interpretation of the data obtained. One of the most powerful tool for achieving quality control of chemical analysis is to use reference materials (RMs) and certified reference materials (CRMs). These materials are necessary for one or more of the following items: method validation (CRMs), monitoring of the state of statistical control (RMs), samples in inter-comparisons (RMs), etc. The requirements and use of RMs and CRMs in chemical analysis are described, with special emphasis on environmental analysis, and some examples of environmental materials currently in production within the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission are given.     

Lead isotopic compositions of environmental certified reference materials for an inter-laboratory comparison of lead isotope analysis.

Lead isotope ratios, viz. 207Pb/206Pb and 208Pb/206Pb, of the commercially available certified reference materials (CRMs) issued in Japan are presented with an objective to provide a data set, which will be useful for the quality assurance of analytical procedures, instrumental performance and method validation of the laboratories involved in environmental lead isotope ratio analysis. The analytical method used in the present study was inductively coupled plasma quadrupole mass spectrometry (ICPQMS) preceded by acid digestion and with/without chemical separation of lead from the matrix. The precision of the measurements in terms of the relative standard deviation (RSD) of triplicated analyses was 0.19% and 0.14%, for 207Pb/20Pb and 208Pb/206Pb, respectively. The trueness of lead isotope ratio measurements of the present study was tested with a few CRMs, which have been analyzed by other analytical methods and reported in various literature. The lead isotopic ratios of 18 environmental matrix CRMs (including 6 CRMs analyzed for our method validation) are presented and the distribution of their ratios is briefly discussed.     

Certified reference materials for the quality control of measurements in environmental monitoring

The monitoring and protection of the environment are based on measurement campaigns which cover long periods of time and large geographical areas. Only accurate analytical results allow valid conclusions to be drawn about a situation and its evolution. The use of certified reference materials (CRMS) permits verification of the accuracy of the measurements. The importance of accuracy and the way CRMs may be used are presented in this review. The production and properties required of a good CRM are discussed. An overview of the types of CRMs in the non-nuclear field, available for the monitoring of the environment, is also given.     

Preparation and certification of creatinine and urea reference materials with certified purity as a traceability source in clinical chemical measurements

Purity certified reference materials (CRMs) are playing a key role in metrological traceability, because they form the basis for many traceability chains in chemistry. Recently, the National Metrology Institute of Japan (NMIJ) has developed two purity CRMs for creatinine (NMIJ CRM 6005-a) and urea (NMIJ CRM 6006-a), because the concentrations of these two compounds are frequently measured in clinical laboratories for monitoring the renal functions. In the certification of purity CRMs, it is essential that the materials have been thoroughly characterized for purity, and the purity should preferably be determined directly by a primary method of measurements. In the development of these two CRMs, we used the purified materials as candidates. The certified values were assigned based on the results of two different methods; acidimetric titration and nitrogen determination by the Kjeldahl method. Since both methods cannot distinguish some impurities from the target compounds, major impurities in the candidate materials were also identified, quantified, and subtracted. These CRMs can provide a traceability link between routine clinical methods and SI units. Presented at BERM-11, October 2007, Tsukuba, Japan.     

Trends in certified reference materials for the speciation of trace elements.

The measurement of the chemical species of elements (instead of the total element concentration) has become an irreversible trend in analytical chemistry. The motivation lies in the fact that the biochemical and geochemical behaviour of an element is governed by its species. Quality assurance of the analytical procedures used for speciation analysis requires the analysis of representative reference materials, certified for the relevant species. Up to now the number of existing certified reference materials for trace element species is very limited. The most important ones are environmental CRMs certified for trialkyltin compounds, methylmercury, Cr(III)/Cr(VI) and food CRMs certified for arsenic species and methylmercury. Major developments are to be expected in CRMs focussed on environmental problems, including waste treatment, on bioavailability of trace elements in food and on bio-monitoring in occupational health and hygiene. It is, however, unlikely that the producers of CRMs will ever be able to cover all needs. Add to this that many, very active species are notoriously unstable and/or short living and require in-situ analysis. This will lead to different analytical developments, such as analyses in-situ, where the classical concept of CRMs may not stand firm anymore.     

k0-NAA quality assessment by analysis of different certified reference materials using the KAYZERO/SOLCOI software

A suite of natural matrix reference materials (RMs) were used to assess the quality of analytical results obtained by k ₀-instrumental neutron activation analysis (k ₀-INAA) at the Joef Stefan Institute (IJS). Five certified reference materials (CRMs) from the Institute for Reference Materials and Measurements (IRMM), two standard reference materials (SRMs) from the National Institute of Standards and Technology (NIST), three RMs from the International Atomic Energy Agency (IAEA) and one RM from IJS were analyzed. Altogether, results for twenty-four elements in inorganic matrices and twenty-nine elements in organic matrices, obtained by k ₀-INAA, were compared to certified values. Results obtained show good agreement with certified or assigned values except for Fe, La, Nd, Sm and U in inorganic matrices, and Ag, Al and Cr in organic matrices.     

Some considerations regarding reference materials and their role in environmental monitoring. Plenary lecture.

After a brief introduction indicating the principal function of reference materials (RMs) in ensuring that the analytical measurement programme is performing reliably, the availability, different types and sources of information on RMs are described. Next, the correspondence of available RMs to present sample demands is discussed, particularly with regard to the adequacy of matrices and analytes, the availability of RMs for 'difficult' trace elements, and the preparation and certification of speciation RMs. The role of RMs in quality control is indicated, and their usage and certain problems which can thereby arise, including total dissolution, homogeneity and their representativeness in relation to samples, are discussed. The application of truly representative RMs in low-level trace element work, as a means of quality control of sampling and storage procedures, is mentioned. Strategies open to the analyst in the total absence of certified RMs are presented, and the importance of publication of independent results by alternative methods for such materials, as a means of establishing consensus values, is stressed. In the situation where results for a particular analyte obtained by different groups for the same (but not identical) biomedical or environmental system differ markedly, a progressive multi-stage exchange scheme is proposed, which is designed to reveal whether the differences arise from analytical factors, sampling effects or real system differences.     

Trends in certified reference materials for the speciation of trace elements

The measurement of the chemical species of elements (instead of the total element concentration) has become an irreversible trend in analytical chemistry. The motivation lies in the fact that the biochemical and geochemical behaviour of an element is governed by its species. Quality assurance of the analytical procedures used for speciation analysis requires the analysis of representative reference materials, certified for the relevant species. Up to now the number of existing certified reference materials for trace element species is very limited. The most important ones are environmental CRMs certified for trialkyltin compounds, methylmercury, Cr(III)/Cr(VI) and food CRMs certified for arsenic species and methylmercury. Major developments are to be expected in CRMs focussed on environmental problems, including waste treatment, on bioavailability of trace elements in food and on bio-monitoring in occupational health and hygiene. It is, however, unlikely that the producers of CRMs will ever be able to cover all needs. Add to this that many, very active species are notoriously unstable and/or short living and require in-situ analysis. This will lead to different analytical developments, such as analyses in-situ, where the classical concept of CRMs may not stand firm anymore.     

Comparison of relative INAA and k 0-INAA using soil and sediment reference materials

The objective of this work was to compare the results obtained by the relative INAA and k ₀-INAA methods for the same input parameters (sample mass, nuclear data, net peak area for the same gamma line and the same measurement and same cooling and measurement times). In total eight environmental soil and sediment reference materials (RM) or certified reference materials (CRM) from different producers were analysed. In this work only the recommended or certified values were considered, allowing comparison of the two methods for 30 elements. The results point out that k ₀-INAA possesses superior qualities compared to relative INAA, being insensitive to flux gradients, and independent of recommended/certified values in RMs/CRMs, often used as standards in relative INAA.     

Metallurgical and chemical characterization of copper alloy reference materials within laser ablation inductively coupled plasma mass spectrometry: Method development for minimally-invasive analysis of ancient bronze objects

The chemical composition of ancient metal objects provides important information for manufacturing studies and authenticity verification of ancient copper or bronze artifacts. Non- or minimal-destructive analytical methods are preferred to mitigate visible damage. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) enables the determination of major elements as well as impurities down to lower ppm-levels, however, accuracy and precision of analysis strongly depend on the homogeneity of reference materials used for calibration. Moreover, appropriate analytical procedures are required e.g. in terms of ablation strategies (scan mode, spot size, etc.). This study reviews available copper alloy (certified) reference materials — (C)RMs from different sources and contributes new metallurgical data on homogeneity and spatial elemental distribution. Investigations of the standards were performed by optical and scanning electron microscopy with X-ray spectrometry (SEM-EDX) for the following copper alloy and bronze (certified) reference materials: NIST 454, BAM 374, BAM 211, BAM 227, BAM 374, BAM 378, BAS 50.01-2, BAS 50.03-4, and BAS 50.04-4. Additionally, the influence of inhomogeneities on different ablation and calibration strategies is evaluated to define an optimum analytical strategy in terms of line scan versus single spot ablation, variation of spot size, selection of the most appropriate RMs or minimum number of calibration reference materials.