Standard reference material standardization

Most of the instrumental direct methods, which are employed in routine analyses, are highly matrix-dependent, therefore methods must be validated with certified standard reference materials. Standard plant reference materials (SRMs), with certified elemental contents can be obtained from NIST, National Institute of Standards and Technology of the United States Department of Commerce or from BCR, Community Bureau of Reference, Commission of the European Community (Colinet et al., 1982 Criepink, 1990 Horwitz and Albert, 1991). 

After the measurement stage has been completed the concentrations of determined elements are calculated using calibration curves, multielement standards, standard reference materials, standard addition methods and single comparator approaches. 

Adapted from Y. C. Wu, W. K. Koch, and R. A. Durst, Standard Reference Materials Standardization of pH Measurements, NIST lecial Publication 260-53. Gaithersburg, MD U.S. Department of Commerce. 1988, http //ts.nist.gov/is/hldocs/230/232/SP PlJBUCAnONS/docuiiients/SP260-53-pdf. Updated values from most recent NIST SRM ceriihcates. m B molality (mol solute/kg HjO). 

Sing (see Ref. 207 and earlier papers) developed a modification of the de Boer r-plot idea. The latter rests on the observation of a characteristic isotherm (Section XVII-9), that is, on the conclusion that the adsorption isotherm is independent of the adsorbent in the multilayer region. Sing recognized that there were differences for different adsorbents, and used an appropriate standard isotherm for each system, the standard isotherm being for a nonporous adsorbent of composition similar to that of the porous one being studied. He then defined a quantity = n/nx)s where nx is the amount adsorbed by the nonporous reference material at the selected P/P. The values are used to correct pore radii for multilayer adsorption in much the same manner as with de Boer. Lecloux and Pirard [208] have discussed further the use of standard isotherms. 

With most non-isothemial calorimeters, it is necessary to relate the temperature rise to the quantity of energy released in the process by determining the calorimeter constant, which is the amount of energy required to increase the temperature of the calorimeter by one degree. This value can be detemiined by electrical calibration using a resistance heater or by measurements on well-defined reference materials [1], For example, in bomb calorimetry, the calorimeter constant is often detemiined from the temperature rise that occurs when a known mass of a highly pure standard sample of, for example, benzoic acid is burnt in oxygen. 

Analysis sheet for Simulated Rainwater (SRM 2694a). Adapted from NIST Special Publication 250 Standard Reference Materials Catalog 1995-96, p. 54 U.S. Department of Commerce, Technology Administration, National Institute of Standards and Technology. 

Consider the situation when the accuracy of a new analytical method is evaluated by analyzing a standard reference material with a known )J,. A sample of the standard is analyzed, and the sample s mean is determined. The null hypothesis is that the sample s mean is equal to p. 

Because of the risk of lead poisoning, the exposure of children to lead-based paint is a significant public health concern. The first step in the quantitative analysis of lead in dried paint chips is to dissolve the sample. Corl evaluated several dissolution techniques. " In this study, samples of paint were collected and pulverized with a Pyrex mortar and pestle. Replicate portions of the powdered paint were then taken for analysis. Results for an unknown paint sample and for a standard reference material, in which dissolution was accomplished by a 4-6-h digestion with HNO3 on a hot plate, are shown in the following table. 

The %w/w lead in a lead-based paint Standard Reference Material and in unknown paint chips is determined by atomic absorption using external standards. 

Analysis of Standards The analysis of a standard containing a known concentration of analyte also can be used to monitor a system s state of statistical control. Ideally, a standard reference material (SRM) should be used, provided that the matrix of the SRM is similar to that of the samples being analyzed. A variety of appropriate SRMs are available from the National Institute of Standards and Technology (NIST). If a suitable SRM is not available, then an independently prepared synthetic sample can be used if it is prepared from reagents of known purity. At a minimum, a standardization of the method is verified by periodically analyzing one of the calibration standards. In all cases, the analyte s experimentally determined concentration in the standard must fall within predetermined limits if the system is to be considered under statistical control. 

For example, if a carbonaceous sample (S) is examined mass spectrometrically, the ratio of abundances for the carbon isotopes C, in the sample is Rg. This ratio by itself is of little significance and needs to be related to a reference standard of some sort. The same isotope ratio measured for a reference sample is then R. The reference ratio also serves to check the performance of the mass spectrometer. If two ratios are measured, it is natural to assess them against each other as, for example, the sample versus the reference material. This assessment is defined by another ratio, a (the fractionation factor Figure 48.2). 

National Institute of Standards and Technology (NIST). The NIST is the source of many of the standards used in chemical and physical analyses in the United States and throughout the world. The standards prepared and distributed by the NIST are used to caUbrate measurement systems and to provide a central basis for uniformity and accuracy of measurement. At present, over 1200 Standard Reference Materials (SRMs) are available and are described by the NIST (15). Included are many steels, nonferrous alloys, high purity metals, primary standards for use in volumetric analysis, microchemical standards, clinical laboratory standards, biological material certified for trace elements, environmental standards, trace element standards, ion-activity standards (for pH and ion-selective electrodes), freezing and melting point standards, colorimetry standards, optical standards, radioactivity standards, particle-size standards, and density standards. Certificates are issued with the standard reference materials showing values for the parameters that have been determined. 

Physical or artifactual standards are used for comparison, caUbration, etc, eg, the national standards of mass, length, and time maintained by the National Institute of Standards and Technology (NIST) or the standard reference materials (SRMs) collected and distributed by NIST. Choice of the standard is determined by the property it is supposed to define, its ease of measurement, its stabiUty with time, and other factors (see Fine chemicals). 

Standard reference materials provide a necessary but insufficient means for achieving accuracy and measurement compatibiUty on a national or international scale. Good test methods, good laboratory practices, well-qualified personnel, and proper intralaboratory and intedaboratory quaUty assurance procedures ate equally important. A systems approach to measurement compatibiUty is ikustrated in Figure 2. The function of each level is to transfer accuracy to the level below and to help provide traceabiUty to the level above. Thus traversing the hierarchy from bottom to top increases accuracy at the expense of measurement efficiency. 

Analytical standards imply the existence of a reference material and a recommended test method. Analytical standards other than for fine chemicals and for the NIST series of SRMs have been reviewed (6). Another sphere of activity ia analytical standards is the geochemical reference standards maintained by the U.S. Geological Survey and by analogous groups ia France, Canada, Japan, South Africa, and Germany (7). 

The predorninant method for the analysis of alurninum-base alloys is spark source emission spectroscopy. SoHd metal samples are sparked direcdy, simultaneously eroding the metal surface, vaporizing the metal, and exciting the atomic vapor to emit light ia proportion to the amount of material present. Standard spark emission analytical techniques are described in ASTM ElOl, E607, E1251 and E716 (36). A wide variety of weU-characterized soHd reference materials are available from major aluminum producers for instmment caUbration. 

Vitreous siUca aimealed at 1100°C has been designated NIST Standard Reference Material 739 (LI and L2). Its expansion coefficient, a, may be calculated for 300—700 K from the following expression (144), where Tis the absolute temperature in Kelvin. 

ISCC-NBS Centroid Color Charts, NBS Standard Reference Material No. 2106, National Institute of Standards and Technology, Washiagton, D.C.,... 

Laser based mass spectrometric methods, such as laser ionization (LIMS) and laser ablation in combination with inductively coupled plasma mass spectrometry (LA-ICP-MS) are powerful analytical techniques for survey analysis of solid substances. To realize the analytical performances methods for the direct trace analysis of synthetic and natural crystals modification of a traditional analytical technique was necessary and suitable standard reference materials (SRM) were required. Recent developments allowed extending the range of analytical applications of LIMS and LA-ICP-MS will be presented and discussed. For example ... 

The set of Glass Standard Reference Material NIST SRM 610 - 614 was used for quantification of amount up to 45 trace elements in the synthetic oxide single crystals and natural quartzites. 

NAA is a quantitative method. Quantification can be performed by comparison to standards or by computation from basic principles (parametric analysis). A certified reference material specifically for trace impurities in silicon is not currently available. Since neutron and y rays are penetrating radiations (free from absorption problems, such as those found in X-ray fluorescence), matrix matching between the sample and the comparator standard is not critical. Biological trace impurities standards (e.g., the National Institute of Standards and Technology Standard Rference Material, SRM 1572 Citrus Leaves) can be used as reference materials. For the parametric analysis many instrumental fiictors, such as the neutron flux density and the efficiency of the detector, must be well known. The activation equation can be used to determine concentrations ... 

Vapor-phase decomposition and collection (Figs 4.16 to 4.18) is a standardized method of silicon wafer surface analysis [4.11]. The native oxide on wafer surfaces readily reacts with isothermally distilled HF vapor and forms small droplets on the hydrophobic wafer surface at room temperature [4.66]. These small droplets can be collected with a scanning droplet. The scanned, accumulated droplets finally contain all dissolved contamination in the scanning droplet. It must be dried on a concentrated spot (diameter approximately 150 pm) and measured against the blank droplet residue of the scanning solution [4.67-4.69]. VPD-TXRF has been carefully evaluated against standardized surface analytical methods. The user is advised to use reliable reference materials [4.70-4.72]. 

Because of the complex nature of the discharge conditions, GD-OES is a comparative analytical method and standard reference materials must be used to establish a unique relationship between the measured line intensities and the elemental concentration. In quantitative bulk analysis, which has been developed to very high standards, calibration is performed with a set of calibration samples of composition similar to the unknown samples. Normally, a major element is used as reference and the internal standard method is applied. This approach is not generally applicable in depth-profile analysis, because the different layers encountered in a depth profile of ten comprise widely different types of material which means that a common reference element is not available. 

The authors demonstrated the importance that correct use of the MDGC-IRMS System is essential for the achievement of precise and accurate measurements. Table 10.4 reports the GC-IRMS measurements of some standard reference materials, obtained with different cut conditions. As can be seen from this table, premature cuts result in 8 C values which are significantly higher than the true values, while delayed cuts give lower 8 C values. This fact indicates that the beginning of the peak is enriched in C, while the end is depleted. 

Table 10.4 GC-IRMS measurements of standard reference materials obtained under different cut conditions (25)...

Many of these are also available as BCS Certified Reference Materials (CRM) supplied by the Bureau of Analysed Samples Ltd, Newham Hall, Middles borough, UK, who also supply EURONORM Certified Reference Materials (ERCM), the composition of which is specified on the basis of results obtained by a number of laboratories within the EEC. BCS Reference Materials are obtainable from the Community Bureau of Reference, Brussels, Belgium. In the USA similar reference materials are supplied by the National Bureau of Standards. 

The following British Chemical Standard or Euronorm Certified Reference Materials may be used for practice in this determination BCS No. 402 ECRM 084-1. 

Throughout this book the use of a number of standard analytical samples is recommended in order that practical experience may be gained on substances of known composition. In addition, standard reference materials of environmental samples for trace analysis are used for calibration standards, and pure organic compounds are employed as standard materials for elemental analysis. 

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