Calibration with certified reference materials

The most economic way of using CRMs for calibration purposes is to validate a procedure for routine analysis. The analytical procedure is carried out with the CRMs analysed as samples. IMth the results achieved, all relevant analytical parameters can be determined, e.g. uncertainty, recovery, reproducibility, selectivity, linearity, etc. The procedure is then well known for the specific sample type and the specific analytes for which it is validated and can be applied routinely for this analytical problem, with a few regular reviews of the analytical performance. CRMs in this case are not used for calibration but rather for validation of the procedure and regular review of the method performance. 

Inductively Coupled Plasma Mass Spectrometry Handbook 

This is stUl considered today as the reference isotope ratio measurement method, as the processes are nearly completely understood. However, due to the ease of use and accessibility of most of the elements, ICP-MS is now preferably applied and the number of projects based on isotope ratio measurements is clearly on the increase. 

When performing isotope ratio measurements, especially with ICP-MS, the following points have to be considered  

Dead time effects for pulse counting detectors 

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Stoll et al. [142] have described a rapid continuous-flow determination of total inorganic carbon in seawater samples. The method runs on an autoanalyser Traacs 800 spectrophotometric system and is calibrated versus certified reference materials readily available. A typical analysis speed of 45 samples per hour can be reached with an accuracy of 2-3 xM and a precision of 2.5 xM. 

Starting with the calibration, the certified reference material can be used as a calibrant (directly or via working standards prepared using them) and in this way traceability of the results to the property values of the certified reference material is ensured. Thus this is a very valid way for certified reference materials to improve the measurements in a laboratory. 

Conventional XRF analysis uses calibration by regression, which is quite feasible for known matrices. Both single and multi-element standards are in use, prepared for example by vacuum evaporation of elements or compounds on a thin Mylar film. Comparing the X-ray intensities of the sample with those of a standard, allows quantitative analysis. Depending on the degree of similarity between sample and standard, a small or large correction for matrix effects is required. Calibration standards and samples must be carefully prepared standards must be checked frequently because of polymer degradation from continued exposure to X-rays. For trace-element determination, a standard very close in composition to the sample is required. This may be a certified reference material or a sample analysed by a primary technique (e.g. NAA). Standard reference material for rubber samples is not commercially available. Use can also be made of an internal standard,... 

Quantification is usually achieved by a standard addition method, use of labeled internal standards, and/or external calibration curves. In order to allow for matrix interferences the most reliable method for a correct quantitation of the analytes is the isotope dilution method, which takes into account intrinsic matrix responses, using a deuterated internal standard or carbon-13-labeled internal standard with the same chemistry as the pesticide being analyzed (i.e., d-5 atrazine for atrazine analysis). Quality analytical parameters are usually achieved by participation in interlaboratory exercises and/or the analysis of certified reference materials [21]. 

Stability of calibrants and analytes is another frequently overlooked aspect of quality assurance, which is particularly relevant to surfactants. This aspect is discussed in Chapter 4.4. Very few intercalibration studies have been performed for the surfactant types of analytes (cf. Chapter 4.5). Currently, no certified reference material is available for surfactants. The European Commission has recently tendered for production of a reference material with certified surfactant concentrations [2]. We can conclude that quality assurance in quantitative surfactant analysis is still in its infancy when compared to analysis of PCB or chlorinated dioxins. Notwithstanding this, several important achievements have been made during recent years regarding improvement of the accuracy and reliability of qualitative analysis of surfactants, which will be the subject of the following chapters. 

Since certified reference materials for seawater nutrient analysis are currently unavailable, individual laboratories must prepare their own standard solutions for instrument calibration. Standard stock solutions are prepared at high concentrations (mM) so that they can be used for months without significant alterations in concentration. Working low-concentration standard solutions are unstable and need to be prepared daily by diluting stock solutions with distilled water or low-nutrient seawater. In this case, the accuracy of nutrient analysis at a given laboratory is highly dependent upon the accuracy of the daily preparation of the calibration solutions. 

Certified reference materials (CRMs) are mainly applied to validate the analytical procedure developed for routine analysis in order to determine the accuracy of analytical data, the recovery for selected elements, the uncertainty of trace element determination and the detection limits. Otherwise, in solid-state mass spectrometric techniques, such as SSMS, LA-ICP-MS, GDMS, SNMS or SIMS, one point calibration using CRMs has been established as an important calibration strategy to obtain reliable analytical data. The one point calibration is performed using the experimentally determined relative sensitivity coefficients (RSCs) on a suitable CRM with a similar trace/matrix composition. An RSC of a chemical element is defined as the ratio of the measured element concentration (experimentally determined) divided by the certified element concentration (accepted or recommended value of element concentration) in a given matrix. 

Calibration with standards that are traceable to NIST-certified reference materials... 

Historically, there have been several ways of demonstrating metrological linkages of traceability. One of the earliest was for a reference laboratory to calibrate an artifact by measuring it and then provide it, along with certified results, to one or more laboratories so that they could also measure it and then compare their results with those of the reference laboratory. Later, distribution of certified reference materials, produced in lots by reference laboratories, provided an exactly analogous linkage for those kinds of materials amenable to production and certification in lots. 

Analyses are performed in accordance with standardized methods issued under the responsibility of a Technical Committee within the Health Ministry. Usually such measurements rely on a comparison of the measured quantity in the unknown sample with the same quantity in a standard , i.e. an RM, according to a specific measurement equation [6], after calibrating the instrument. Calibration of a photometric system for clinical analyses usually means the set of operations that establish, under specific conditions, the relationship, within a specified range, between values indicated by the instrument and the corresponding values assigned to the RMs at the stated uncertainty. Calibration of the photometer itself implies the calibration of wavelength and absorbance scale by means of proper wavelength and absorbance RMs [5], traceable to national standards. A calibration of the instrument is still needed in concentration units to check the indicated provided value. The measurement result is then verified by application of that method of measurement to a certified reference material (CRM). Both the comparator - a photometric device with narrow or wide bandwidth, and the RMs should thus be validated. 

In this scheme, the primary reference material is defined as a chemical substance of the highest (and known) purity, or a well-characterized substance in a matrix, This classification of materials is, however, fairly arbitrary. It is ideal when used in connection with standards characterized in terms of biological activity. Primary standards are thus the International Reference Preparations (IRP) produced by the World Health Organization (WHO). In this case the primary standard for a particular antibiotic is the WHO reference preparation which constitutes the unit of that antibiotic. When people wish to use it they have to prepare a large batch of samples calibrated to the primary. This is then called a secondary standard. However, for well-defined chemical parameters, the term certified reference material is preferred. 

An analyst needs to calibrate an atomic absorption spectrophotometer used for the determination of lead in milk samples. The analyst can purchase a certified reference material (CRM) solution of lead in nitric acid. This CRM is used to prepare a set of calibration standard solutions of known concentration of lead. These calibration standards, along with a suitable blank material (see Section 5.4), are used to calibrate the instrument. 

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