Preparation and characterization of organic calibration solutions for development of certified reference materials at the National Metrology Institute of Japan

Certified reference materials (CRMs) are playing an increasingly important role in environmental monitoring in Japan. The National Metrology Institute of Japan (NMIJ)/National Institute of Advanced Industrial Science and Technology (AIST) has been developing CRMs of organic calibration solutions since 2003, and has issued several NMIJ CRMs. The development of these materials was conducted at the NMIJ in cooperation with candidate material producers. The freezing-point depression method was principally adopted for assessment of the purity of starting materials to give reliable certified values. Gas chromatography with flame ionization detection (GC–FID) and/or high-performance liquid chromatography (HPLC), which are based on independent principles and whose levels of accuracy are well evaluated, were applied in combination with other methods to avoid any possible analytical bias. Purity assessment is outlined for two typical examples, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (p,p′-DDD) and 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′-DDT), which were used as starting materials for a CRM under development. Methods adopted for gravimetric preparation and ampouling of solutions were qualified and optimized to reduce the uncertainties of certified values due to these factors. Furthermore, a new experimental scheme for assessment of stability and preparation variation is proposed for the proper estimation of uncertainties. Presented at BERM-11, October 2007, Tsukuba, Japan.     

The role of reference materials in food analysis

Reliability and accuracy of measurements in food and agricultural materials are essential both for implementation of the legislation concerning public health and consumer protection and for the elimination of disputes arising from trade requirements and technical barriers. In such process the crucial step is represented by the programmes aimed at the quality assurance of analytical data produced by laboratories involved in food analysis. In this framework a major role is played by the proper use of reference materials. This report provides an overview on relevance, availability, use, certification procedures and perspective of reference materials in food analysis. Measurement harmonization procedures are also discussed.     

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     

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.

Reference materials and certified reference materials for water and food microbiology

Summary The concept of Certified Reference Materials (CRMs) for the verification of the accuracy of analytical methods and the traceability of the results to a CRM, is well accepted in chemistry. The use of Reference Materials (RMs) for intra-laboratory quality control schemes or for round-robin and proficiency testing is well established and follows from certain norms (ISO 9000 and EN 45000 series). For microbiology such concepts have not been fully defined and RMs are only rarely used. CRMs do not exist. To fill this gap the Commission of the European Community, through the BCR programme, has launched projects in collaboration with the RIVM (National Institute of Public Health and Environmental Protection) in Bilthoven (NL). Following fundamental considerations and feasibility studies, several intercomparisons have been held using selected laboratories working with food or water microbiology. Various microbiological strains have been subject of studies: Salmonella typhimurium, Listeria monocytogenes, Bacillus cereus, Staphylococcus aureus for food, Escherichia coli, Enterococcus faecium, Enterobacter cloacae and Staphylococcus warneri for water. To produce materials for interlaboratory studies, a set of milk powders was prepared by spray-drying. Separate portions were contaminated with one of the strains mentioned. The materials were then encapsuled in gelatine. It has been demonstrated that if protected in milk powder matrices, bacteria maintain the ability to be revived, but do not multiply. The modes of evaluation of the results for homogeneity and stability differ from those commonly used in chemistry.     

Statistical aspects of the use of reference materials

Summary Interlaboratory testing, even when coupled with careful calibrations in terms of SRM's, is a complex process. It often raises problems that only the subject-matter specialists can solve. The problems are definitely not solved by rejecting test results or laboratories.     

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     

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.     

Development of food reference materials for nutritional analysis

Summary The development of five reference materials for major nutritional properties, whole milk powder, pork muscle, wheat and rye flour, and haricots verts beans is described. Homogeneity and stability of these materials proved to be adequate. A preliminary intercomparison of methods showed that results for total fat and total dietary fibre were method dependent. Evaluation of methods used for available carbohydrates revealed poor solubilisation and hydrolysis of starch in some laboratories. This intercomparison has given valuable information for the final certification of these materials.     

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     

Iodine in different food articles and standard reference materials

Summary The greater part of essential iodine enters living organisms via the food chain. Nevertheless, quantitative data on its concentration in diets, food articles and also in available SRMs are very poor and scarce. This and WHO recommendations on daily allowances of iodine for man via food articles caused an added demand for accurate and reliable determination of iodine in these samples. From this point of view the purpose of the present was to analyse and to establish the concentration levels of total iodine in some food articles, diets, SRMs and candidate reference materials by the use of rapid radiochemical separation, developed in our laboratory. The results were checked by the analysis of SRMs with available certified values for iodine and good agreement is evident.     

Criteria for the development of biological reference materials

Summary A review is presented of factors to be considered in the development of biological reference materials. Some guidelines are offered regarding approaches to the generation of the varied materials required for analytical quality control. Major considerations in such an endeavour are the goal of the undertaking and role of the final product, selection of candidate materials, preparation, characterization and certification. Selection of materials should be from those important to commerce and consumers, and related to various regulatory, clinical, environmental, and research activities. They should adequately represent the different choices and types of foodstuffs, clinical materials and environmental materials, such as soils, sewage sludges, plant and animal tissues, of interest in different regions of the world.Acquisition can be from commercial sources or the result of in-house preparation, with attention to stability enhancement if required and maintenance of native analyte levels by minimization of contamination. The approach to chemical and physical characterization relies on the measurement philosophy, selection of analytes, their speciation, and selection of analytical methods and analysts for establishment of homogeneity and quantitative levels. Throughout the overall task of RM development there is a requirement for a critical approach by critical analytical and measurement scientists and the involvement of national RM agencies in order to produce top quality control materials.

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Kriterien für die Entwicklung von biologischen Referenzmaterialien

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Contribution No. 88-50 from Land Resource Research Centre     

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.     

The certification of major components and major elements in five food reference materials

Summary The development of five food reference materials (whole milk powder, pork muscle, rye and wheat flour, and haricot beans) is described. Homogeneity and stability of three categories of nutrients, major components, major elements and vitamins, proved to be adequate. Certification of Kjeldahl nitrogen, total fat, lactose, total dietary fibre (AOAC method), ash, Na, K, Mg, Ca, and Cl contents was successful. In contrast, only indicative values could be given for starch and sugars, nonstarch polysaccharides and P because of insufficient agreement between laboratories. The measurement of these components and elements need further study to obtain the improvement needed. Indicative values for retinol, -carotene, -tocopherol, vitamin B₁, vitamin C, and niacin in some of these materials could be given. Prospects for future certification of vitamins are favourable.     

Research and development on activation analysis at the Thailand Institute of Nuclear Technology

Research and development in activation analysis at the Thailand Institute of Nuclear Technology has been carried out over 40 years. The main activation source is from the TRIGA type research reactor TRR1/M1. Average in-core flux is around 10¹³ n·cm⁻²·s⁻¹. Experience on the analysis of various kind of samples range from environmental field especially air particulate, ores, rocks and soil for natural resources exploration as well as industrial applications. Elemental composition in silk thread, silk cocoon and silk products from the royal silk project are one of the research work done incorporation with the Queen Sirikit Institute of Sericulture. Food items are also another topic of interest to our research team.     

Stability studies of vitamins in three food reference materials

Summary Stability in storage and shipment of retinol, -tocopherol, vitamins B₁, B₂ and C in three foods was studied to assess the feasibility of certifying the vitamin content of three food RMs, whole milk powder (CRM 380), pork muscle (CRM 384) and freeze-dried haricot beans (CRM 383); these were recently certified for major dietary components and major elements. Interpretation of the long-term stability data was complicated by a dominant analytical variability over the measurement period. The long-term stability study (24 months) gave evidence of deterioration of vitamin B₂ in pork muscle. The other vitamins studied seemed to be acceptably stable at –18°C and +4°C. Additional studies showed stability of retinol in milk powder for 34 months and of vitamin C in haricot beans for 31 months at –18°C and +4°C. Long-term storage seems to be possible at a temperature not higher than +4°C except for vitamin B₂. A short-term stability study at +25°C and +30°C for 6 weeks showed acceptable stability of retinol and -tocopherol in milk powder (CRM 380) and of vitamin C in haricot beans (CRM 383). However, storage at +42°C induces degradation of retinol, -tocopherol and vitamin C.     

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.     

Allergen determination in food: reference materials and traceability of results

Food allergens are more or less denatured mixtures of non-defined proteins in complex matrices. The most common technique to measure these proteins is an antibody-based system as, e.g., a commercial ELISA system which consists of an extraction procedure, suitable antibodies and a calibrator. Until now, only a few attempts to standardize these different ELISA systems were performed and the most promising way seems to be a standardization of the calibrator. It is shown that we have currently no methods to fully characterize these calibrators, which are always complex protein mixtures. This also means that the production of reference materials containing these calibrators is not possible. It is proposed to choose a different way because we will never have an unbroken traceability chain. As described in ISO 17511:2003 for the clinical area, one possibility could be the selection of a commercial preparation (e.g. skim milk powder) to which all test kit manufacturers will relate their results on and in a second step to select a reference method.