Quality-control materials in the USDA National Food and Nutrient Analysis Program (NFNAP)

The US Department of Agriculture (USDA) Nutrient Data Laboratory (NDL) develops and maintains the USDA National Nutrient Databank System (NDBS). Data are released from the NDBS for scientific and public use through the USDA National Nutrient Database for Standard Reference (SR) (). In 1997 the NDL initiated the National Food and Nutrient Analysis Program (NFNAP) to update and expand its food-composition data. The program included: 1) nationwide probability-based sampling of foods; 2) central processing and archiving of food samples; 3) analysis of food components at commercial, government, and university laboratories; 4) incorporation of new analytical data into the NDBS; and 5) dissemination of these data to the scientific community. A key feature and strength of the NFNAP was a rigorous quality-control program that enabled independent verification of the accuracy and precision of analytical results. Custom-made food-control composites and/or commercially available certified reference materials were sent to the laboratories, blinded, with the samples. Data for these materials were essential to ongoing monitoring of analytical work, to identify and resolve suspected analytical problems, to ensure the accuracy and precision of results for the NFNAP food samples.     

Summary of reference materials for the determination of the nutrient composition of foods

Certified reference materials (CRMs) play a critical role in validating the accuracy of nutrient data for food samples. A number of available food CRMs of differing matrix composition have assigned concentrations for various nutrients, along with associated uncertainty intervals (UIs) for those values. These CRMs have been used extensively in the United States Department of Agriculture’s (USDA) ongoing National Food and Nutrient Analysis Program (NFNAP) to monitor the accuracy of assays of key foods and nutrients consumed in the United States. A total of 690 assigned values for individual nutrients, including proximates, vitamins, macroelements, microelements, fatty acids, amino acids, and selected phytochemicals (e.g., carotenoids), were compiled from the certificates of analysis for 63 CRMs, and the specified UI in each case was expressed as a percentage of the assigned certified or reference concentration. Across all nutrients, 63.5% of the UIs were less than 10% of the assigned value, 25.5% were 10–20%, and 11% were greater than 20% of the assigned value. The UIs for proximates, minerals, and trace elements were most consistently less than 10% of the assigned value. The relative uncertainties were significantly higher for vitamins, suggesting greater challenges in measuring and certifying these components. These high UIs (greater than 10% assigned value) in the best available reference materials are likely to be indicative of the precision and accuracy that can be obtained by current measurement systems for these components. These data suggest that care must be taken in choosing CRMs to monitor food composition analysis, including evaluating what levels of uncertainty are required in assigned values and which analytical measurement systems for food components need closer examination and improvement. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. Presented at ‘BERM-10’, April 2006, Charleston, SC, USA.     

The NIH analytical methods and reference materials program for dietary supplements

Quality of botanical products is a great uncertainty that consumers, clinicians, regulators, and researchers face. Definitions of quality abound, and include specifications for sanitation, adventitious agents (pesticides, metals, weeds), and content of natural chemicals. Because dietary supplements (DS) are often complex mixtures, they pose analytical challenges and method validation may be difficult. In response to product quality concerns and the need for validated and publicly available methods for DS analysis, the US Congress directed the Office of Dietary Supplements (ODS) at the National Institutes of Health (NIH) to accelerate an ongoing methods validation process, and the Dietary Supplements Methods and Reference Materials Program was created. The program was constructed from stakeholder input and incorporates several federal procurement and granting mechanisms in a coordinated and interlocking framework. The framework facilitates validation of analytical methods, analytical standards, and reference materials.     

Development of candidate reference materials for the measurement of lead in bone

The production of modest quantities of candidate bone lead (Pb) reference materials is described, and an optimized production procedure is presented. The reference materials were developed to enable an assessment of the interlaboratory agreement of laboratories measuring Pb in bone; method validation; and for calibration of solid sampling techniques such as laser ablation ICP-MS. Long bones obtained from Pb-dosed and undosed animals were selected to produce four different pools of a candidate powdered bone reference material. The Pb concentrations of these pools reflect both environmental and occupational exposure levels in humans. The animal bones were harvested post mortem, cleaned, defatted, and broken into pieces using the brittle fracture technique at liquid nitrogen temperature. The bone pieces were then ground in a knife mill to produce fragments of 2-mm size. These were further ground in an ultra-centrifugal mill, resulting in finely powdered bone material that was homogenized and then sampled-scooped into vials. Testing for contamination and homogeneity was performed via instrumental methods of analysis.

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.

鱼肉环丙沙星标准样品的研制

介绍了以鲤鱼鱼肉作为基质含有环丙沙星的标准样品的研制过程。通过添加环丙沙星养殖鲤鱼获得样品,用液相色谱-串联质谱法对样品进行均匀性和稳定性检测,采取8个实验室协作定值的方法对样品进行定值检测,进行了标准值的计算和不确定度评估;研究表明获得的样品均匀性良好,稳定性至少17个月,可以用于检测质量控制和科研工作。     

Method validation and reference materials

For implementation of food and feed legislation, there is a strong need for development and harmonisation of reliable, validated and if possible, robust and simple analytical methods. In addition, precise methods used for measuring the exposure of humans to certain types of food contaminants and residues (natural, man-made or produced during technological treatment) such as, e.g. mycotoxins, acrylamide, pesticides and allergens have to be available, in order to compare results derived from monitoring studies. Methods should be validated (in-house or in a collaborative trial) according to harmonised protocols and good laboratory practice must be in place in order to be compliant with internationally harmonised standards. The way in which this is implemented depends strongly on the analyte, interference within the food matrix and other requirements that need to be met. Food and feed certified reference materials, when matrix matched and containing the appropriate concentration of the certified substance, are an extremely useful tool in validation of measurements.Presented at BERM-9—Ninth International Symposium on Biological and Environmental Reference Materials, 15–19 June 2003, Berlin, Germany.     

Reference materials for the radionuclide program – performance evaluation samples

 The U.S. Food and Drug Administration's (FDA) Radionuclides in Food Program was reinstituted in 1973, expanded in 1975 and again in 1990, to its present status. The need for reference materials for radionuclides in food samples was recognized as early as 1962. There were no available reference materials for these types of samples at that time. The materials developed to assure that the results being obtained were acceptable were primarily milk, water and food. The radionuclides of interest were iodine-131, cesium-137 and other short-lived radionuclides found in fission products. These were first issued through the then Health, Education and Welfare Department's Analytical Quality Control Program and, later, in 1970 through the Environmental Protection Agency (EPA). In November 1998, the EPA discontinued this program. The FDA is proposing to reinstitute part of this program, as a primary laboratory, traceable to the National Institute of Technology (NIST) and included in this, the FDA proposes to supply the States and/or their contractors with low-level standards and with milk- and water intercomparison samples. It will also use these results where possible as collaborative studies to validate some of the more recent methods adopted by the American Society for Testing and Materials (ASTM), American Public Health Association (APHA) and Association of Official Analytical Chemists International (AOAC, Int'l.) The FDA will also supply low-level standards to compliment these programs as did the EPA. It is expected that these samples will serve as performance evaluation samples for the States programs.     

Sediment certified reference materials for the determination of polychlorinated biphenyls and organochlorine pesticides from the National Metrology Institute of Japan (NMIJ)

Two marine sediment certified reference materials, NMIJ CRM 7304-a and 7305-a, have been issued by the National Metrology Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) for the determination of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). The raw materials of the CRMs were collected from a bay near industrial activity in Japan. Characterization of these CRMs was conducted by NMIJ, where the sediments were analyzed using multiple analytical methods such as pressurized liquid extraction (PLE), microwave-assisted extraction (MAE), saponification, Soxhlet extraction, supercritical fluid extraction (SFE), and ultrasonic extraction; the target compounds were determined by one of the primary methods of measurements, isotope dilution–mass spectrometry (ID-MS). Certified values have been provided for 14 PCB congeners (PCB numbers 3, 15, 28, 31, 70, 101, 105, 138, 153, 170, 180, 194, 206, 209) and 4 OCPs (γ-HCH, 4,4′-DDT, 4,4′-DDE, 4,4′-DDD) in both CRMs. NMIJ CRM 7304-a has concentrations of the contaminants that are a factor of 2–15 greater than in CRM 7305-a. Both CRMs have information values for PCB homolog concentrations determined by collaborative analysis using a Japanese official method for determination of PCBs. The total PCB concentrations in the CRMs are approximately 920 and 86 μg kg⁻¹ dry mass respectively. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Standard reference materials for foods and dietary supplements

Well-characterized certified reference materials are needed by laboratories in the food testing, dietary supplement, and nutrition communities to facilitate compliance with labeling laws and improve the accuracy of information provided on product labels, so that consumers can make good choices. As a result of the enactment of the Nutrition Labeling and Education Act of 1990 and the Infant Formula Act of 1980, the National Institute of Standards and Technology (NIST) worked to develop a series of food-matrix standard reference materials (SRMs) characterized for nutrient concentrations. These include SRM 1544 Fatty Acids and Cholesterol in a Frozen Diet Composite, SRM 1546 Meat Homogenate, SRM 1548a Typical Diet, SRM 1566b Oyster Tissue, SRM 1846 Infant Formula, SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue, SRM 2383 Baby Food Composite, SRM 2384 Baking Chocolate, SRM 2385 Slurried Spinach, and SRM 2387 Peanut Butter. With the enactment of the Dietary Supplement Health and Education Act of 1994, NIST has been working to develop suites of dietary supplement SRMs characterized for active and marker compounds and for toxic elements and pesticides, where appropriate. An updated SRM 1588b Organics in Cod Liver Oil, a suite of ephedra-containing materials (SRMs 3240–3245), a carrot extract in oil (SRM 3276), and a suite of ginkgo-containing materials (SRMs 3246–3248) are available. Several other materials are currently in preparation. Dietary supplements are sometimes provided in forms that are food-like; for these, values may also be assigned for nutrients, for example SRM 3244 Ephedra-Containing Protein Powder. Both the food-matrix and dietary supplement reference materials are intended primarily for validation of analytical methods. They may also be used as “primary control materials” in assignment of values to in-house (secondary) control materials to confirm accuracy and to establish measurement traceability to NIST.     

Matrix materials for proficiency testing: optimization of a procedure for spiking soil with gamma-emitting radionuclides

The IAEA Reference Materials Group of the Chemistry Unit, Agency’s Laboratories Seibersdorf, has developed and optimized a procedure for spiking some environmental matrices with gamma-emitting radionuclides. This paper describes the spiking procedure, homogeneity testing of the spiked material, and assignment of property values and their associated uncertainties for the radionuclides ⁵⁴Mn, ⁶⁵Zn, ⁶⁰Co, ¹⁰⁹Cd, ¹³⁴Cs, ¹³⁷Cs, ²¹⁰Pb, and ²⁴¹Am. This procedure has already been successfully used in an IAEA proficiency test on the determination of ¹³⁷Cs and ²¹⁰Pb in spiked soil and has been found to be appropriate for production of soil materials for proficiency testing and internal quality control samples. The main advantage of this procedure is a low uncertainty arising from heterogeneity, which was found to be less than 1.2% for all the analytes studied.      

Update on COMAR: the Internet database for certified reference materials

This paper describes the COMAR database for certified reference materials (CRMs). The Web-based version of COMAR is freely accessible via the Internet. COMAR was established to assist laboratories in finding the CRMs needed. The database is maintained in a collaboration of the world’s major CRM producers. The planned changes in the database as agreed at the last COMAR council meeting in Prague in May 2006 are indicated.

Clinical reference materials for the validation of the performance of photometric systems used for clinical analyses

 There are a wide variety of spectrophotometric devices nowadays used in health services with various qualities of manufacture methods of measurement and metrological characteristics for performing the necessary measurements. Therefore, to meet the accuracy and repeatability requirements needed in medical diagnosis and treatment, the validation of the performance of such systems by clinical chemistry laboratories is essential. However, the validation of a spectrophotometric system for clinical analyses requires several reference materials, according to the end use of the measurement results. This paper discusses some characteristics required of the clinical reference materials needed and used by Romanian Institute of Metrology for validation work. Types of clinical reference materials developed in the national area for this purpose are also presented. Received: 23 April 1997 · Accepted: 7 July 1997     

Challenges in preparing water-matrix reference materials for PAHs and pesticides: examples from SWIFT-WFD proficiency-testing schemes

In accordance with Article 8 of the European Union (EU) Water Framework Directive (WFD), EU Member States are required to establish monitoring programs for the quality of the surface water and the groundwater within each river-basin district. As such data are the basis for regulatory decisions and measures required to achieve WFD environmental objectives, appropriate analytical quality-assurance and quality-control tools have to be implemented by the monitoring laboratories. In this respect, reference materials (RMs) play a key role. Within the framework of the SWIFT-WFD project (Screening methods for Water data InFormation in support of the WFD), several approaches to the preparation of matrix RMs for the analysis of polycyclic aromatic hydrocarbons and pesticides in water have been used in wide-scale proficiency-testing (PT) schemes. We present the different strategies employed in preparing water-matrix RMs for organic analytes. By reviewing the results from the SWIFT-WFD PT schemes, we reflect on the applicability and the suitability of the different approaches.     

The reference materials syndrome

This paper examines specific cases in the literature where analysts using spectroscopic instrumentation report elemental concentrations that agree with information values reported in reference material certificates that are subsequently found to be incorrect.     

Mineral oil certified reference materials for the determination of polychlorinated biphenyls from the National Metrology Institute of Japan (NMIJ)

Four mineral oil certified reference materials (CRMs), NMIJ CRM 7902-a, CRM 7903-a, CRM 7904-a, and CRM 7905-a, have been issued by the National Metrology Institute of Japan, which is part of the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST), for the determination of polychlorinated biphenyls (PCBs). The raw materials for the CRMs were an insulation oil (CRM 7902-a and CRM 7903-a) and a fuel oil (CRM7904-a and CRM 7905-a). A solution of PCB3, PCB8, and technical PCB products, comprising four types of Kaneclor, was added to the oil matrices. The total PCB concentrations in the PCB-fortified oils (CRM 7902-a and CRM 7904-a) are approximately 6 mg kg⁻¹. In addition, the mineral oils which were not fortified with PCBs were also distributed as CRMs (CRM 7903-a and CRM 7905-a). Characterization of these CRMs was conducted by the NMIJ/AIST, where the mineral oils and the PCB solution were analyzed using multiple analytical methods such as dimethylsulfoxide extraction, normal-phase liquid chromatography, gel permeation chromatography, reversed-phase liquid chromatography, and chromatography using sulfoxide-bonded silica; and/or various capillary columns for gas chromatography, and two ionization modes for mass spectrometry. The target compounds in the mineral oils and those in the PCB solution were determined by one of the primary methods of measurement, isotope dilution–mass spectrometry (ID-MS). Certified values have been provided for 11 PCB congeners (PCB3, 8, 28, 52, 101, 118, 138, 153, 180, 194, and 206) in the CRMs. These CRMs have information values for PCB homologue concentrations determined by using a Japanese official method for determination of PCBs in wastes and densities determined with an oscillational density meter. Because oil samples having arbitrary PCB concentrations between respective property values of the PCB-fortified and nonfortified CRMs can be prepared by gravimetric mixing of the CRM pairs, these CRMs can be used for validation of PCB analyses using various instruments which have different sensitivities. Figure Preparation and certification processes of the mineral oil CRMs (example shown is polychlorinated biphenyls in insulation oil, high/low concentrations) Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The establishment of a quality evaluation system of reference materials

Reference materials have been applied widely to ensure the traceability, comparability and reliability of measurement results. To achieve this purpose, the quality of reference materials (RMs) themselves is surely an important aspect to be pay attention to. A quality evaluation system of RMs has been established through the project “The National Sharing Platform of Reference Materials” in China to give a reliable assessment on the quality of RMs from various sources including the accuracy and comparability of their property values, which is very useful to promote the appropriate selecting and using of RMs in China. Through the application of National Metrology Institute calibration and measurement capabilities on the basis of the international mutual recognition arrangement, it can also provide a powerful supplement to the current activities such as the accreditation of RM producers in the construction of a global harmonized quality control and assurance system of RMs.     

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.     

Quality assurance in biological monitoring of environmental exposure to pollutants: from reference materials to external quality assessment schemes

The presence of chemicals in the environment is a matter of concern in that it poses potential health risks. At present, exposure to toxic chemicals and their biological and biochemical effects can be better estimated by biological monitoring, through the systematic collection of specimens from potentially exposed humans. Biological monitoring of human exposure to environmental pollutants is hampered by the difficulty to assess data reliability. As a consequence, the validity of biological monitoring should depend on the strict implementation of a quality assurance (QA) program, which includes a series of procedures aiming to ensure that laboratory results meet defined standards of quality and are reliable. For the validation and monitoring of methods’ performance, to ensure the trueness of measurements and to warrant the traceability to international standards, reference materials (RMs) and certified reference materials should be used. Internal quality control and external quality assessment (EQA) are part of overall QA and are carried out to verify that analytical errors are compatible with the specific requirements or needs of the user. In particular EQA schemes (EQAS) allow to test independently the analytical performance of participating laboratories. In the last decades, increasing concern has been raised by urban air pollution; lead and benzene, two gasoline components released by motor vehicle exhausts, are known to be toxic to humans. For biological monitoring of lead exposure of the general population, screening campaigns, utilizing lead in blood as a biomarker, have been carried out since the 1970s. Strict strategies were adopted to ensure data comparability, including the preparation of RMs, the organization of EQAS and the cross-exchange and analysis of blood samples between laboratories. Biological monitoring of benzene exposure could be carried out by means of various biomarkers such as benzene in blood and benzene, trans,trans-muconic acid (t,t-MA) and S-phenylmercapturic acid (S-PMA) in urine. At present, few RMs and EQAS are available for these biomarkers. A pilot EQAS for t,t-MA in urine, adopted to assess the reliability of data regarding benzene exposure, has been organized and carried out between 1996 and 1997 in Italy. From the accrued experience, it clearly emerges the importance of strategies designed to guarantee the quality of biological monitoring data. The use of RMs and the participation in EQAS are highly recommended in order to improve the global performance of methods and laboratories involved in biological monitoring.