Application of synthetic reference materials in the medical radiological research centre

The contents of 21 chemical elements (Ag, Br, Ca, Cl, Co, Cr, Cs, Fe, Hg, K, Mg, Mn, Na, P, Rb, Sb, Sc, Se, Sr, Zn, Zr) in synthetic reference materials (SRMs) were compared with those in natural reference materials (NRMs) using short- and long-lived radionuclides. SRMs called synthetic standards (SSs) and synthetic standards, biological (SSBs) were prepared on the basis of phenol-formaldehyde resol resins in the Institute of Physics, Georgian Academy of Science. The NRMs included such IAEA reference materials as H-4 (animal muscle), A-13 (animal blood), H-5 (animal bone), SL-1 (lake sediment), SOIL-7 (soil), A-9 (mixed human diet), and IAEA-153 (milk powder). It was shown that SSB-SRMs possessed good representativity of the 30–50 mg tablets, high precision, operational convenience, and could be recommended for the INAA of a wide range of medico-biological and bioecological objects.     

Determination of polybrominated diphenyl ethers in environmental standard reference materials

Standard reference materials (SRMs) are valuable tools in developing and validating analytical methods to improve quality assurance standards. The National Institute of Standards and Technology (NIST) has a long history of providing environmental SRMs with certified concentrations of organic and inorganic contaminants. Here we report on new certified and reference concentrations for 27 polybrominated diphenyl ether (PBDE) congeners in seven different SRMs: cod-liver oil, whale blubber, fish tissue (two materials), mussel tissue and sediment (two materials). PBDEs were measured in these SRMs, with the lowest concentrations measured in mussel tissue (SRM 1974b) and the highest in sediment collected from the New York/New Jersey Waterway (SRM 1944). Comparing the relative PBDE congener concentrations within the samples, we found the biota SRMs contained primarily tetrabrominated and pentabrominated diphenyl ethers, whereas the sediment SRMs contained primarily decabromodiphenyl ether (BDE 209). The cod-liver oil (SRM 1588b) and whale blubber (SRM 1945) materials were also found to contain measurable concentrations of two methoxylated PBDEs (MeO-BDEs). Certified and reference concentrations are reported for 12 PBDE congeners measured in the biota SRMs and reference values are available for two MeO-BDEs. Results from a sediment interlaboratory comparison PBDE exercise are available for the two sediment SRMs (1941b and 1944).     

Resolution of discrepant analytical data in the certification of platinum in two automobile catalyst SRMs

The National Institute of Standards and Technology (NIST) recently developed two recycled automobile catalyst materials as standard reference materials (SRMs), in response to a request from the International Precious Metals Institute. Results of analyses for platinum by two different analytical techniques did not agree well, with the means differing up to 6%. The palladium results for these same two techniques in the same materials showed much better agreement. Finally, it was determined that one technique (instrumental neutron activation analysis — INAA) had a small, random interference due to a tantalum impurity in/on the acid washed polyethylene bag used to hold the finely powdered sample. This Ta was not present in any of the empty bags used to evaluate the bag blank. Once this problem was identified, the unique characteristics of the INAA technique allowed the magnitude of the interference to be accurately determined for each sample, data recalculated, and a final result obtained which agreed well with the second technique.     

Use of reference materials in coastal monitoring quality assurance

The NOAA National Status and Trends (NS&T) Program determines the current status of, and changes over time in the environmental health of U.S estuarine and coastal waters. Concentrations of organic and inorganic contaminants are determined in bivalves, bottom-dwelling fish and sediments. The quality of the analytical data generated by the NS&T Program is over-seen by the performance-based Quality Assurance Project, which is designed to document sampling protocols, analytical procedures, and laboratory performance, and to reduce intralaboratory and interlaboratory variation. All NS&T cooperating laboratories are required to participate in yearly intercomparison exercises. The analysis of reference materials, such as the National Research Council of Canada's Certified Reference Materials (CRMs) and National Institute of Standards and Technology's (NIST) Standard Reference Materials (SRMs), and of control materials, is required. Because of the need for marine matrix reference materials and standards, NOAA contributed to the production of eight NIST SRMs and seven internal standard solutions. Analytical data from all control materials and all matrix reference materials are reported to the Program office.     

Determination of perfluorinated alkyl acid concentrations in biological standard reference materials

Standard reference materials (SRMs) are homogeneous, well-characterized materials used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of SRMs that have mass fraction values assigned for legacy pollutants. These SRMs can also serve as test materials for method development, method validation, and measurement for contaminants of emerging concern. Because inter-laboratory comparison studies have revealed substantial variability of measurements of perfluoroalkyl acids (PFAAs), future analytical measurements will benefit from determination of consensus values for PFAAs in SRMs to provide a means to demonstrate method-specific performance. To that end, NIST, in collaboration with other groups, has been measuring concentrations of PFAAs in a variety of SRMs. Here we report levels of PFAAs and perfluorooctane sulfonamide (PFOSA) determined in four biological SRMs: fish tissue (SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue), bovine liver (SRM 1577c), and mussel tissue (SRM 2974a). We also report concentrations for three in-house quality-control materials: beluga whale liver, pygmy sperm whale liver, and white-sided dolphin liver. Measurements in SRMs show an array of PFAAs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Reference and information values are reported for PFAAs measured in these biological SRMs.

Standard Reference Materials to support US regulations for nutrients and contaminants in food and dietary supplements

To address the measurement and standard needs of the food and nutrition communities, the National Institute of Standards and Technology (NIST) has developed a suite of food-matrix Standard Reference Materials (SRMs) characterized for nutrient concentrations. These food-matrix SRMs include infant formula, baby food, and typical diet composites; meat homogenate, oyster, mussel, and fish tissues; baking chocolate; peanut butter; and spinach. Many of these materials were developed based on recommendations of the food industry to populate a nine-sectored triangle, developed by the Association of Analytical Communities (AOAC) International, in which foods are positioned based on their fat, protein, and carbohydrate contents. Value assignment of proximates, vitamins, and elements of nutritional interest in these food-matrix SRMs has been based primarily on the combination of results from measurements at NIST and from a group of collaborating laboratories involved in food measurements. Food-matrix SRMs are now available that are representative of all nine sectors of the AOAC International food-matrix triangle. Current activities are focused on the development of SRMs for dietary supplements including botanical and multivitamin/multielement materials.Presented at the CCQM Workshop on Comparability and Traceability in Food Analysis, 18–19 November 2003, BIPM, Sèvres, France.     

Separation of 26 toxaphene congeners and measurement in air particulate matter SRMs compared to technical toxaphene SRM 3067

Toxaphene is a complex technical mixture that has been found ubiquitously in the environment but has caused issues for analysis, especially of individual congeners. This paper reports the elution order of 26 major toxaphene congeners on three gas chromatographic columns. The three different stationary phases generally had similar elution orders for the toxaphene congeners, but fewer co-elutions occurred on a low-bleed, low-polarity column. These congeners (except for two that co-eluted and were not added to the calibration mixture) were examined in air particulate matter standard reference materials (SRMs), 1648a, 1649a, and 1649b as well as SRM 3067 toxaphene in methanol for assignment of reference values. SRM 3067 had mass fractions an order of magnitude greater than the air particulate SRMs, which ranged from 0.568 ± 0.018 ng g⁻¹ dry mass (B9-2006 in SRM 1648a) to 12.9 ± 0.20 ng g⁻¹ dry mass (B9-715 (P 58) in SRM 1649a). The three air particulate SRMs all had different mass fractions and proportions of congeners relative to the sum of the toxaphene congeners. SRM 3067 may be useful as a technical mixture toxaphene congener calibrant. SRMs 1648a and 1649b will serve as reference materials for the analysis of 21 (three congeners were not included due to values below the detection limit or a potential polychlorinated biphenyl co-elution) toxaphene congeners in atmospheric particulate samples.     

Reflections on 35 years of biological SRM production and analyses

Summary During the author's 39 years with the National Bureau of Standards (NBS)/National Institute for Standards and Technology (NIST) as an employee, and since then as Guest Researcher, he has been intimately involved with biological Standard Reference Material (SRM) production and analyses. His involvement with biological reference materials started with the very first biological certified reference material (CRM), the SRM 1571, Orchard Leaves, initiated in 1968 and issued in 1971, through the latest material (SRM 1575a, Pine Needles - renewal), issued in 2003. In addition, for more than 20 years he was Technical Coordinator for botanical SRMs for the NBS/NIST Analytical Chemistry Division. This paper contains his historical reflections and highlights from those years, and includes the techniques used to obtain and process these materials, new developments and procedures that resulted in vastly improved reference materials, the application of high accuracy neutron activation analysis to the certification of these standards, and the trace element quality assurance vital to the accuracy of these standards.     

Simultaneous determination of inorganic mercury,methylmercury, and total mercury concentrations in cryogenic fresh-frozen and freeze-dried biological reference materials

Two speciated isotope dilution (SID) approaches consisting of a single-spike (SS) method and a double-spike (DS) method including a reaction/transformation model for the correction of inadvertent transformations affecting mercury species were compared in terms of accuracy, method performance, and robustness for the simultaneous determination of methylmercury (MeHg), inorganic mercury (iHg), and total mercury (HgT) concentrations in five biological Standard Reference Materials (SRMs). The SRMs consisted of oyster and mussel tissue materials displaying different mercury species concentration levels and different textural/matrix properties including freeze-dried (FD) materials (SRMs 1566b, 2976, and 2977) and cryogenically prepared and stored fresh-frozen (FF) materials (SRMs 1974a, 1974b). Each sample was spiked with (201)iHg (Oak Ridge National Laboratory, ORNL) and Me(202)Hg (Institute for Reference Materials and Measurements. IRMM-670) solutions and analyzed using alkaline microwave digestion, ethylation, and gas chromatography inductively coupled plasma mass spectrometry (GC/ICP-MS). The results obtained by the SS-SID method suggested that FF and FD materials are not always commutable for the simultaneous determination of iHg, MeHg, and HgT, due to potential transformation reactions resulting probably from the methodology and/or from the textural/matrix properties of the materials. These transformations can occasionally significantly affect mercury species concentration results obtained by SS-SID, depending on the species investigated and the materials considered. The results obtained by the DS-SID method indicated that the two classes of materials were commutable. The simultaneous and corrected concentrations of iHg, MeHg, and HgT obtained by this technique were not found to be statistically different form the certified and reference concentration together with their expanded uncertainty budgets for the five SRMs investigated, exemplifying the robustness, the accuracy, and the improved commutability of this method compared to SS-SID measurements.     

Erste Ergebnisse einer Ringanalyse zur Erstellung eines internen Buchenblatt-Referenzmaterials für ?kosystemuntersuchungen

Summary To evaluate pollution effects on ecosystems, more and more plant and animal samples are analyzed for their concentrations of pollutants and nutrient elements. Since chemical analyses of biological materials are largely influenced by matrix effects, their accuracy depends on the availability of reference materials. Unfortunately only very few such standards exist so far. The described interlaboratory comparison of beech leaves from Baden-Württemberg demonstrates the possibility of producing reference materials from selected organisms, which — though not certified — are sufficient for research projects. Apart from their function as reference materials, those standards show typical levels of elemental concentrations for their region of origin. First results are introduced.     

Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants

Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10–20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Certification strategies for health-related SRMS at NIST

Inaccuracy in health-related measurements raises overall health care costs, results in misdiagnoses, leads to inaccurate conclusions in clinical studies, and results in inaccurate nutrition labeling. NIST has an extensive program aimed at providing the health measurements community with standard reference materials (SRMs) to assist them in making accurate measurements. A variety of approaches are used to certify health-related SRMs. For pure crystalline SRMs used as primary standards, direct assays of purity are often not possible. Thus numerous techniques including differential scanning calorimetry, mass spectrometry, chromatography, and others may be used to assess purity. For matrix SRMs used to assess the accuracy of measurement systems, the approaches for certification depend upon the needs of the users and NIST capabilities. When accuracy needs are the highest and the methods exist, NIST uses definitive methods, primarily involving isotope dilution mass spectrometry. These methods have been applied to the certification of serum-based SRMs for a number of the common clinical analytes. For many analytes, definitive methods have not been developed, so NIST uses other strategies for certification. In some cases, such as for drugs of abuse, two independent methods are used for the measurements. For nutrients such as vitamins, in-house methods are used along with results from outside laboratories having extensive experience with a particular analysis. The paper includes tables with examples of many of the health-related SRMs that are available. Received: 15 May 1997 / Revised: 23 July 1997 / Accepted: 25 July 1997     

Traceability of performance evaluation materials

One of the most critical elements of a performance evaluation (PE) program for radioactivity measurements is the traceability of the PE materials to the national standards. The requirements and criteria for the production of traceable environmental and radiobioassay PE materials have been defined by ANSI N42.22 and ANSI N13.30 standards. It is important to note that use of traceable source materials does not necessarily ensure the traceability of subsequently derived PE materials unless verification measurements exist in conjunction with the preparation processes. This paper describes the protocol currently used by NIST for the preparation and verification of air filter, acidified water, spiked soil, synthetic urine, and synthetic fecal PE materials for low-level radioactivity measurements. The process involves gravimetric dilutions and mixing of primary radionuclide NIST Standard Reference Materials (SRMs), addition of the derived master solution to sample matrices, and subsequent verification measurements. Several gamma-emitters were used to trace the gravimetric dilutions and spike addition through an unbroken chain of gamma comparison measurements. The massic activities of alpha- and beta-emitters in the diluted solutions and PE samples were also measured by radiochemical methods and compared with their gravimetric values. A correlation analysis demonstrated that the gamma emitters quantitatively followed ⁹⁰Sr, ²³⁸U, ²³⁸Pu, and ²⁴¹Am throughout the dilution and spiking and can be used as effective process monitors. The statistical results from t-tests, box plots, and normal probability tests suggested that traceability of radionuclides in the PE materials to their primary standards can be verified to within 1%, with an overall precision better than 2% (1s).     

Determination of caffeine and caffeine-related metabolites in ephedra-containing standard reference materials using liquid chromatography with absorbance detection and tandem mass spectrometry

The concentrations of caffeine and caffeine-related compounds in 2 ephedra-containing reference materials have been determined by 3 independent methods with measurements performed by the National Institute of Standards and Technology (NIST) and a collaborating laboratory. Results from the 3 methods were used for value assignment of caffeine, theobromine, and theophylline in these Standard Reference Materials (SRMs). The methods used at NIST to determine the concentration levels of caffeine, theobromine, and theophylline in SRM 3243 Ephedra-Containing Solid Oral Dosage Form and SRM 3244 Ephedra-Containing Protein Powder used reversed-phase liquid chromatography with absorbance detection and tandem mass spectrometry. These reference materials are part of the first suite in a series of NIST SRMs that provide concentration values for multiple components in dietary supplements. These SRMs are primarily intended for method validation and for use as control materials to support the analysis of dietary supplements and similar materials.     

Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry

Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n = 3, 1σ). A good agreement between experimental results and the certified values was also observed.     

Determination of perfluorinated alkyl acid concentrations in human serum and milk standard reference materials

Standard Reference Materials (SRMs) are certified reference materials produced by the National Institute of Standards and Technology that are homogeneous materials well characterized with values for specified properties, such as environmental contaminant concentrations. They can be used to validate measurement methods and are critical in improving data quality. Disagreements in perfluorinated alkyl acid (PFAA) concentrations measured in environmental matrices during past interlaboratory comparisons emphasized the need for SRMs with values assigned for PFAAs. We performed a new interlaboratory comparison among six laboratories and provided, for the first time, value assignment of PFAAs in SRMs. Concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other PFAAs in two human serum and two human milk SRMs are reported. PFAA concentration measurements agreed for serum SRM 1957 using different analytical methods in six laboratories and for milk SRM 1954 in three laboratories. The interlaboratory relative standard deviation for PFOS in SRM 1957 was 7%, which is an improvement over past interlaboratory studies. Matrix interferences are discussed, as well as temporal trends and the percentage of branched vs. linear isomers. The concentrations in these SRMs are similar to the present-day average concentrations measured in human serum and milk, resulting in representative and useful control materials for PFAA human monitoring studies.     

Developing qualitative LC-MS methods for characterization of Vaccinium berry Standard Reference Materials

Standard Reference Materials (SRMs) offer the scientific community a stable and homogenous source of material that holds countless application possibilities. Traditionally, the National Institute of Standards and Technology (NIST) has provided SRMs with associated quantitative information (certified values) for a select group of targeted analytes as measured in a solution or complex matrix. While the current needs of the SRM community are expanding to include non-quantitative data, NIST is attempting to broaden the scope of how and what information is offered to the SRM community by providing qualitative information about biomaterials, such as chromatographic fingerprints and profiles of untargeted identifications. In this work, metabolomic and proteomic profiling efforts were employed to characterize a suite of six Vaccinium berry SRMs. In the discovery phase, liquid chromatography-tandem mass spectrometry (LC-MS/MS) data was matched to mass spectral libraries; a subsequent validation phase based on multiple-reaction monitoring LC-MS/MS relied on both retention time matching of authentic standards along with fragmentation data for a qualitative overview of the most prominent organic compounds present. Definitive and putative identifications were determined for over 70 metabolites based on reporting guidelines set forth by the Metabolomics Standards Initiative (Metabolomics 3(3):211–221, 2007), and the capability of electrospray ionization mass spectrometry (ESI-MS) to profile untargeted metabolites within a complex matrix using mass spectral matching is demonstrated. Bottom-up proteomic analyses were possible using peptide databases translated from expressed sequence tags (ESTs). Homology searches provided identification of novel Vaccinium proteins based on homology to related genera. Chromatographic fingerprints of these berry materials were acquired for supplemental qualitative information to be provided to users of these SRMs. An unbounded set of qualitative data about a biomaterial is a valuable complement to quantitative information traditionally provided in NIST Certificates of Analysis.     

Three new mussel tissue standard reference materials (SRMs) for the determination of organic contaminants

Three new mussel tissue standard reference materials (SRMs) have been developed by the National Institute of Standards and Technology (NIST) for the determination of the concentrations of organic contaminants. The most recently prepared material, SRM 1974b, is a fresh frozen tissue homogenate prepared from mussels (Mytilus edulis) collected in Boston Harbor, Massachusetts. The other two materials, SRMs 2977 and 2978, are freeze-dried tissue homogenates prepared from mussels collected in Guanabara Bay, Brazil and Raritan Bay, New Jersey, respectively. All three new mussel tissue SRMs complement the current suite of marine natural-matrix SRMs available from NIST that are characterized for a wide range of contaminants (organic and inorganic). SRM 1974b has been developed to replace its predecessor SRM 1974a, Organics in Mussel Tissue, for which the supply is depleted. Similarly, SRMs 2977 and 2978 were developed to replace a previously available (supply depleted) freeze-dried version of SRM 1974a, SRM 2974, Organics in Freeze-Dried Mussel Tissue. SRM 1974b is the third in a series of fresh frozen mussel tissue homogenate SRMs prepared from mussels collected in Boston Harbor starting in 1988. SRM 1974b has certified concentration values for 22 polycyclic aromatic hydrocarbons (PAHs), 31 polychlorinated biphenyl congeners (PCBs), and 7 chlorinated pesticides. Reference values are provided for additional constituents: 16 PAHs, 8 PCBs plus total PCBs, 6 pesticides, total extractable organics, methylmercury, and 11 trace elements. PAH concentrations range from about 2 ng g^–1 dry mass (cyclopenta[cd]pyrene) to 180 ng g^–1 dry mass (pyrene). PCB concentrations range from about 2 ng g^–1 dry mass (PCB 157) to 120 ng g^–1 dry mass (PCB 153). The reference value for total PCBs in SRM 1974b is (2020 ± 420) ng g^–1 dry mass. Pesticide concentrations range from about 4 ng g^–1 dry mass (4,4-DDT) to 40 ng g^–1 dry mass (4,4-DDE). SRM 2977 has certified values for 14 PAHs, 25 PCB congeners, 7 pesticides, 6 trace elements, and methylmercury. Reference values for 16 additional PAHs and 9 inorganic constituents are provided, and information values are given for 23 additional trace elements. SRM 2978 has certified and reference concentrations for 41 and 22 organic compounds, respectively, and contains contaminant levels similar to those of SRM 1974b. Organic contaminant levels in SRM 2977 (mussels from Guanabara Bay, Brazil) are typically a factor of 2 to 4 lower than those in SRM 1974b and SRM 2978. The organic contaminant concentrations in each new mussel tissue SRM are presented and compared in this paper. In addition, a chronological review of contaminant concentrations associated with mussels collected in Boston Harbor is discussed as well as a stability assessment of SRM 1974a.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Assessment of stability of trace elements in two natural matrix environmental standard reference materials: NIST-SRM 1547 Peach leaves and NIST-SRM 1566a Oyster Tissue

The NIST program for environmental Standard Reference Materials (SRM) includes materials covering a range of matrices, mass fraction values and analytes. For many SRMs, mass fraction data are accumulated, incidentally, over time, as these are used routinely for quality assurance purposes. Although these are not formal stability studies, data generated may be useful in assessing stability. To evaluate the potential for assessing material stability from incidental use of SRMs, results of neutron activation analysis performed from 1992 through 2008 were compiled for SRM 1547 Peach Leaves and SRM 1566a Oyster Tissue. Results indicate that incidental use of SRMs yields useful information on SRM stability.