Implementation of ISO Guide 34: Accreditation for reference material production

The National Analytical Reference Laboratory of the Australian Government Analytical Laboratories was initially accredited to ILAC Guide G 12:2000 in January 2000 and is currently accredited to ISO Guide 34 (2000) for the production of a range of pure organic substance reference materials. This paper discusses the practical challenges and rewards of developing and implementing a quality system for reference material production and discusses some of the barriers, and potential solutions, to more general implementation of third-party accreditation.     

Production of reference material

Summary Carbon has been determined in the certified reference sample Euro CRM Pure Iron 097-1 to 3.98 g C/g (R = 0.15 at P = 95%) by combustion of the sample portion with subsequent indication of the CO₂ by coulometry. A calibration material based on primary sources of carbon was used with a sufficient small interval of uncertainty of the accuracy and an adequate weighing system. The blank could be kept sufficiently small with a fraction of 23% of the total analytical signal. The surface carbon of the 097-1 was determined to approximately 50% of the total carbon. This result of total carbon is considerably lower than the values in the certificate reading up to 20 g/g. This reflects the strong tendency to too high values in the certificates of reference steels with contents of carbon up to 100 g/g. Examples are given.

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Herstellung von Referenzmaterial — Bestimmung von Kohle in Stählen und reinem Eisen im Bereich von 1–100 g/g mit primärer Kalibrierung

     

Production of standard reference material

Summary Deviations were reproduced repeatedly between certified and observed low phosphorus values in commercial standard reference steel samples when being analyzed thoroughly by photometry of the yellow phosphorus vanadato molybdenum complex after extraction by methyl isobutyl ketone. The values observed were by 14 ppm (min 2, max 26) lower as certified. The accuracy of these results on a choice of those samples was achieved and proved by primary calibration with pure substances with an interval of uncertainty of only 1.4ppm (95% confidence interval). As demonstrated this fact demands imparatively the documented application of primary calibration substances and suitable calibration methods when standard reference material is produced.

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Zur Herstellung von StandardreferenzmaterialÜberprüfung des Phosphorgehaltes in Standardreferenzstählen im Bereich von 59–125 ppm P durch Primäreichung

Zusammenfassung Aufgrund von wiederholten und reproduzierbaren Abweichungen zwischen den Soll- und Ist-Gehalten niedriger Phosphorwerte in käuflichen Standardreferenzstählen wurde eine Auswahl dieser Proben sorgfältig durch Photometrie des gelben Phosphorvanadatomolybdänkomplexes nach MIBK-Extraktion untersucht. Die Richtigkeit der Ergebnisse, die etwa 14 ppm (min. 2, max. 26) unter den Angaben der Zertifikate liegen, wurde durch Primäreichung mit Reinsubstanzen mit einem Unsicherheitsbereich von nur 1,4 ppm (P=95%) nachgewiesen. Dieser Sachverhalt legt, wie gezeigt wird, die dokumentierte Anwendung von primären Eichsubstanzen und geeigneten Eichmethoden bei der Untersuchung künftiger Standardreferenzproben zwingend nahe.

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The author thanks E. Weichert for efficient assistance with the practical work.     

Production of certified reference material

Summary Carbon has been determined in 31 European reference steels in the range of 11–2561 g/g C, using an absolute calibration method.High-purity calcium carbonate was used as the calibration material and weighing was carried out by means of a balance with extremely small weighing error. Both synthetic calibration samples and test samples were processed alternatingly under identical conditions, and the analyses were completed in the shortest possible time.In 28 of the cases examined, results were lower than the certificate values, by an average of 27 g/g. The interval of uncertainty of the accuracy was 6 g/g (probability 99%).

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Herstellung zertifizierter ReferenzmaterialienGenaue Bestimmung von Kohlenstoff in Stählen im Bereich von 11–2561g/g

Zusammenfassung Die Kohlenstoffgehalte von 31 europäischen zertifizierten Referenzstählen im Arbeitsbereich von 11–2561 g/g Kohlenstoff wurden durch absolute Eichung überprüft.Die hinreichende Reinheit des Eichmittels Calciumcarbonat wurde sichergestellt und ein Wägesystem mit einem hinreichend kleinen Wägefehler benutzt.Das gleiche Verhalten von synthetischen Eichproben und Analysenproben im Analysenprozeß wurde hergestellt und beide Probearten wechselweise unter konstanten Systembedingungen innerhalb kürzester Zeitspanne untersucht. In 28 der untersuchten Fällen wurden im Mittel um 27 ppm tiefere Werte gefunden als in den Zertifikaten angegeben. Das Unsicherheitsintervall der Richtigkeit der gefundenen Werte lag mit einer Wahrscheinlichkeit von 99% im Mittel bei 6 g/g.

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Abbreviations CRM Certified reference material - ppm g/g The author thanks Mr. E. Weichert for his excellent direction of the practical work.     

Accreditation of reference material producers

 The use of reference materials is the most pragmatic means by which the analyst can achieve comparability of data. Reference material producers therefore need to have adequate quality systems in place for ensuring the reliability of their materials. In order to provide guidance to both producers and assessors, ISO Guide 34 has recently been produced detailing the quality system requirements for the production of reference materials. CITAC, REMCO and ILAC are now collaborating in the revision of this guide to produce a free-standing document detailing the general requirements for the competence of reference material producers. This paper discusses some of the more important issues described in these documents. The possible formation of an international register containing details of a reference material producer's quality system status is also discussed.     

A pilot study for the production of a certified reference material for trace elements in honey

In the context of the general mandate of the European Union Community Reference Laboratory (CRL) for residues in living animals and their products established at the Istituto Superiore di Sanità, a pilot study was undertaken to assess the possibility of producing a new certified reference material (CRM) for trace elements in a matrix of honey. The elements considered were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V and Zn. Their determination was performed by inductively coupled plasma (ICP)-based techniques. Data obtained with different ICP techniques were generally in good agreement. In light of these results, the next step was the effective production of a candidate CRM in a honey matrix. In the preliminary phase, two different types of honey, i.e., Eucalyptus (solid and sticky) and Robinia (viscous and sticky), were pretreated at the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (EC-JRC-IRMM) in order to produce the materials candidate for the certification process. Approximately 600 ampoules were thus produced for the Robinia honey and 450 ampoules for the Eucalyptus honey, each ampoule containing 5 g of an aqueous solution of honey (with 20% and 30% high purity water, respectively) and sealed under inert gas (Ar). A ring test to determine the levels of the chemical elements and a long-term study to evaluate the stability of the samples is in progress. Tentative figures for the analytes of interest are (in ng g⁻¹): Robinia, As, 1.28±0.09; Cd, 0.59±0.08; Cr, 2.36±0.21; Cu, 57.6±3.2; Fe, 209±9; Mn, 90.8±3; Ni, 18.1±0.6; Pb, 23±1.5; Sn, 8.10±0.35; V, 1.19±0.37; and Zn, 178±4; Eucalyptus, As, 3.18±0.21; Cd, 0.70±0.08; Cr, 2.73±0.22; Cu, 141±6; Fe, 926±16; Mn, 1905±81; Ni, 7.77±0.4; Pb, 138±4; Sn, 7.97±0.16; V, 3.47±0.15; and Zn, 405±9.     

Experience with wheat flour reference material

The Chemical Section of the National Office of Measures, Hungary (OMH) [1] embarked on the preparation of a wheat sample series as a Certified Reference Material [2] (CRM) in 1992. The practical implementation of the wheat sample series has shown that test- ing laboratories are in great need of easy-to-use flour reference samples to objectively and independently qualify wheat. To fill this need, we have developed a three-term flour reference sample series. The certification process was car-ried out according to ISO recommendations. Investigations of the long-term stability [3] and the application of wheat and flour CRMs are continuing. Wheat is one of the most widely grown crops in Hun- gary and it is one of the major determinative factors in the economy. Its uniform and objective qualification is of outstanding importance. There are well-equipped laborato-ries with sufficient experience to assess wheat flour quality, howev- er, proficiency testing has shown that certified samples need to be used to achieve exact and uniform measuring results. Received: 12 November 1999 Accepted: 16 August 2000     

Preparation of a lichen reference material

For preparation of a multielement lichen reference material for environmental studies, 25 kg of the epyphitic lichen Evernia prunastri (L.) Ach. was collected in unpolluted regions of Portugal. The lichen was removed from Cistus ladanifer and Quercus spp. The material was ground to a mesh size 125 m. The material homogeneity was evaluated by determining Na, K, Mn, Br, As, La and Sm on two samples of 100 mg taken at each of 20 locations of the bulk material; the locations were randomly chosen. The k₀-based INAA was used. The material is homogeneous for fractions 100 mg, as shown by the evaluation of the heterogeneity of the subsampling operation in the 20 locations and by the results of a one-way analysis of variance for the data obtained. The composition of Evernia prunastri varies neither with the region where it grows nor with the date of collection. This work was accomplished under contract with the IAEA.     

Need for food reference material in Latin America

Summary Even if some Latin American countries still need to extend their capacity for food quality control, many do have good control laboratories and high quality research institutions. That makes the need for reference material in Latin America similar to that of other parts of the world.The region has special problems related to mail and shipment delays, and to the lack of information on available reference material. It is recommended that additional reference material being made available for vitamins in food, for polar and non-polar organophosphorus pesticides in vegetables, for organophosphorus pesticide and veterinary drugs in meat etc.Reference material should simulate real samples as closely as possible; reference samples for water should contain phthalates which in environmental samples interfere with organochlorines and reference material for organophosphates in vegetables should contain metabolites and degradation products.It is also recommended that commercial standards for trace metals should have the production date and the guaranteed stability printed on the label. Information on reference material should be included in the methods published by AOAC, AOCS and similar publications.     

水中氯离子溶液标准物质的研制

以氯化钠纯度标准物质为原料,超纯水为溶剂,采用重量–容量法制备了水中氯离子溶液标准物质,系统阐述了水中氯离子溶液标准物质的研制方法.采用离子色谱法对制备的水中氯离子溶液标准物质进行分析,通过F–检验和回归曲线法对色谱数据进行计算,方差分析和线性拟合结果表明该溶液标准物质具有良好的均匀性和稳定性.研制的水中氯离子溶液标准...     

异辛烷中正十六烷溶液标准物质制备

以正十六烷和异辛烷为原料,采用重量–容量法制备异辛烷中正十六烷溶液标准物质。经过均匀性检验、稳定性考察和量值比较,结果表明该标准物质符合国家二级标准物质的研制要求,标准值为500 ng/μL(Urel=2%,k=2),可作为量值传递的标准,用于气相色谱仪的校准和检定、分析方法评价,以及正十六烷的质量控制等方面。该标准物质已取得国家二级标准物质证书,证书编号为GBW(E)130660。     

Examination of a procedure for the production of a simulated filter-based air particulate matter reference material

An approach for producing simulated air particulate matter (APM) deposited on filters has been developed and investigated as to its usefulness for yielding large batches of filters as a future reference material. The APM deposited on the filters was a material collected from an urban industrial area, and had been milled to approximate a material of PM-2.5 particle size distribution. The milled APM material was loaded onto filter substrates (Nuclepore) through the deposition of aliquots from a liquid suspension via vacuum filtration. It should be noted that these filters do not represent a typical PM-2.5 elemental composition, since the milling increased the proportion of crustal materials and the suspension in liquid decreased the sulfate content. Homogeneity between filters was tested using INAA (whole filter analysis) and ED-XRF and PIXE and was estimated to be in the 5% range (relative standard deviation). Homogeneity within the filters and among the filters was also tested using micro-XRF and found to be acceptable for the elements tested. The results of the tests carried out on the filters indicate that this approach is appropriate for large-scale production of similar filters for distribution as reference materials.     

Purity assessment using the mass balance approach for inorganic in-house certified reference material production at Inmetro

Accreditation and Quality Assurance - The production of Certified Reference Materials (CRMs) is one of the essential activities of the National Institute of Metrology, Quality and Technology...     

A new river sediment standard reference material

The collection, processing and certification of a new sediment Standard Reference Material (SRM), SRM 2704, is described. Collected from the bottom of the Buffalo River in New York State during the fall of 1986, SRM 2704 is certified for 25 elements with information provided on another 22 elements. Improvements in analytical methods as well as the application of well-defined quality-control procedures for collection, processing and analysis have resulted in a reference material that is more completely characterized than previous NIST sediment reference materials.     

Water content variation of p-n-heptylphenol reference material

Water content variation of candidate p-n-heptylphenol (HP) reference material (ampoule form) for preparation of a primary standard solution based on the Japan Calibration Service System, a national standards dissemination system, under the Measurement Law of Japan, was examined by a Karl-Fischer water content meter. As prepared samples, liquid-phase HP and upper, middle, and lower layers of solid-phase HP were measured since characteristic phase transition occurs near room temperature (melting point: 28.98 °C). As a result of water content in liquid- and solid-phase HP, water content variation among three layers of solid-phase is found in within ampoules, though water content variation of liquid-phase is not found. Between-ampoule variation of water content is also found using total ampoules of liquid-phase HP used to eliminate within-ampoule variation. Moreover, water content variation is secondarily confirmed by the results of the amount-of-substance fraction of HP based on a differential scanning calorimeter. From these results in this study, it is concluded that within- and between-ampoule variations of water content may depend on phase transition and water loss during ampouling of candidate reference material, respectively.