Analytical procedure accuracy

Analytical procedure Accuracy Repeatability Intermediate precision Specificity Detection limit Quantitation limit Linearity Range Compound(s) Reference(s)... 

Analytical procedures, accuracy, precision and mineral standards... 

The choice between X-ray fluorescence and the two other methods will be guided by the concentration levels and by the duration of the analytical procedure X-ray fluorescence is usually less sensitive than atomic absorption, but, at least for petroleum products, it requires less preparation after obtaining the calibration curve. Table 2.4 shows the detectable limits and accuracies of the three methods given above for the most commonly analyzed metals in petroleum products. For atomic absorption and plasma, the figures are given for analysis in an organic medium without mineralization. 

Although isotope-dilution analysis can be very accurate, a number of precautions need to be taken. Some of these are obvious ones that any analytical procedure demands. For example, analyte preparation for both spiked and unspiked sample must be as nearly identical as possible the spike also must be intimately mixed with the sample before analysis so there is no differential effect on the subsequent isotope ration measurements. The last requirement sometimes requires special chemical treatment to ensure that the spike element and the sample element are in the same chemical state before analysis. However, once procedures have been set in place, the highly sensitive isotope-dilution analysis gives excellent precision and accuracy for the estimation of several elements at the same time or just one element. 

Accurate GDMS analysis has required the development of analytical procedures appropriate to the accuracy and detection limits required and specific to the mate-... 

The function of the analyst is to obtain a result as near to the true value as possible by the correct application of the analytical procedure employed. The level of confidence that the analyst may enjoy in his results will be very small unless he has knowledge of the accuracy and precision of the method used as well as being aware of the sources of error which may be introduced. Quantitative analysis is not simply a case of taking a sample, carrying out a single determination and then claiming that the value obtained is irrefutable. It also requires a sound knowledge of the chemistry involved, of the possibilities of interferences from other ions, elements and compounds as well as of the statistical distribution of values. The purpose of this chapter is to explain some of the terms employed and to outline the statistical procedures which may be applied to the analytical results. 

Even if Eq. (1-6) holds throughout the course of the reaction, an intermediate such as Tl2+ or Fe41- may still be involved, but it remains at a concentration very low compared with those of the reactants and products. A difference between any two terms in Eq. (1-6) represents the concentration of the intermediate, however minute. One s ability to detect the difference depends upon the accuracy of two analyses. A difference once thought to be insignificant may become measurable with the development of a more accurate analytical procedure. 

The accuracy of an analytical procedure expresses the closeness of agreement between the value, which is accepted either as a conventional true value or an accepted reference value and the value found. This Is sometimes termed trueness . 

The quantitation limit of an individual analytical procedure is the lowest amount of analyte in a sample, which can be quantitatively determined with suitable precision and accuracy. 

The range of an analytical procedure is the interval between the upper and lower concentration (amounts) of analyte in the sample (including these concentrations) for which it has been demonstrated that the analytical procedure has a suitable level of precision, accuracy and linearity. 

A soil sample was taken from a field, transported back to the laboratory by road and stored for three weeks prior to analysis. The analytical procedure consisted of drying the soil in an oven at 100°C for 24 h before the analyte was extracted using 200 cm of dichloromethane. This extract was reduced in volume to 200 til and a 20 p.l aliquot then analysed by HPLC. A calibration was set up by measuring the response from a number of solutions containing known concentrations of the analyte. The resnlt obtained from the unknown , after suitable mathematical manipulation, indicated the original soil sample contained 20 0.05 mgkg of the analyte. Comment on the accuracy of this result. 

For the high accuracy needed in the quantitative measmement of the species, quality assurance of the analytical procedures is of prime importance. This can only be achieved by using representative RMs, certified for the relevant species. Up to now the number of existing certified reference materials is very limited. This section will give a survey of the main species that are presently determined routinely or for research purposes. 

In certain areas, particularly the rapidly developing area of organo-metalhc spedation, concern has been expressed that artifacts may lead to false results. One example are the doubts about the accuracy and suspicion of possible artifact formation of methyhner-cury (MeHg) duriri analytical procedures, mainly distillation and alkaline dissolution, which were expressed for the first time at the Conference Mercury as a Global Pollu-tanf in 1996 (Hintelmann and Evans 1997 Hintelmann et al.1997). 

Speciation involves a number of discrete analytical steps comprising the extraction (isolation) of the analytes from a solid sample, preconcentration (to gain sensitivity), and eventually derivatisation (e.g. for ionic compounds), separation and detection. Various problems can occur in any of these steps. The entire analytical procedure should be carefully controlled in such a way that decay of unstable species does not occur. For speciation analysis, there is the risk that the chemical species can convert so that a false distribution is determined. In general, the accuracy of the determinations and the trace-ability of the overall analytical process are insufficiently ensured [539]. 

Analytical methods, particularly those used by accredited laboratories, have to be validated according to official rules and regulations to characterize objectively their reliability in any special field of application (Wegscheider [1996] EURACHEM/WELAC [1993]). Validation has to control the performance characteristics of analytical procedures (see Chap. 7) such as accuracy, precision, sensitivity, selectivity, specificity, robustness, ruggedness, and limit values (e.g., limit of detection, limit of quantitation). 

As a measuring science, analytical chemistry has to guarantee the quality of its results. Each kind of measurement is objectively affected by uncertainties which can be composed of random scattering and systematic deviations. Therefore, the measured results have to be characterized with regard to their quality, namely both the precision and accuracy and - if relevant - their information content (see Sect. 9.1). Also analytical procedures need characteristics that express their potential power regarding precision, accuracy, sensitivity, selectivity, specificity, robustness, and detection limit. 

A quantitative term to describe the (lack of) accuracy of an analytical procedure which comprises the imprecision and the bias. 

The introduction of high-resolution, high-efficiency /-ray detectors composed of lithium-drifted germanium crystals has revolutionised /-measurement techniques. Thus, /-spectrometry allows the rapid measurement of relatively low-activity samples without complex analytical preparations. A technique described by Michel et al. [25] uses Ge(Li) /-ray detectors for the simultaneous measurements of 228radium and 226radium in natural waters. This method simplifies the analytical procedures and reduces the labour while improving the precision, accuracy, and detection limits. 

Derivatization of organic compounds has been traditionally used in organic analysis as additional evidence for structural features, to simplify analytical procedures, to improve the sensitivity or accuracy of the analysis, etc. It is worthwhile recalling briefly the requirements for a good derivatizing scheme that were summarized elsewhere in the Functional Group series1 3, because such schemes will be an important part of the analytical chapters. 

Field samphng, sample transport, and laboratory sampling are the three steps that must be carried out before sample analysis in the laboratory. Not getting a representative sample in the held, transport, and storage under nonideal conditions, and improper sampling in the laboratory can all cause dramatic changes in the results of an analytical procedure and thus alter its accuracy. The effect of these factors on variation in the data obtained is always larger than the inherent accuracy of the actual chemical procedure. 

Whereas precision (Section 6.5) measures the reproducibility of data from replicate analyses, the accuracy (Section 6.4) of a test estimates how accurate the data are, that is, how close the data would represent probable true values or how accurate the analytical procedure is to giving results that may be close to true values. Precision and accuracy are both measured on one or more samples selected at random for analysis from a given batch of samples. The precision of analysis is usually determined by running duplicate or replicate tests on one of the samples in a given batch of samples. It is expressed statistically as standard deviation, relative standard deviation (RSD), coefficient of variance (CV), standard error of the mean (M), and relative percent difference (RPD). 

The accuracy of an analysis can be determined by several procedures. One common method is to analyze a known sample, such as a standard solution or a quality control check standard solution that may be available commercially, or a laboratory-prepared standard solution made from a neat compound, and to compare the test results with the true values (values expected theoretically). Such samples must be subjected to all analytical steps, including sample extraction, digestion, or concentration, similar to regular samples. Alternatively, accuracy may be estimated from the recovery of a known standard solution spiked or added into the sample in which a known amount of the same substance that is to be tested is added to an aliquot of the sample, usually as a solution, prior to the analysis. The concentration of the analyte in the spiked solution of the sample is then measured. The percent spike recovery is then calculated. A correction for the bias in the analytical procedure can then be made, based on the percent spike recovery. However, in most routine analysis such bias correction is not required. Percent spike recovery may then be calculated as follows ... 

Analytical data generated in a testing laboratory are generally used for development, release, stability, or pharmacokinetic studies. Regardless of what the data are required for, the analytical method must be able to provide reliable data. Method validation (Chapter 7) is the demonstration that an analytical procedure is suitable for its intended use. During the validation, data are collected to show that the method meets requirements for accuracy, precision, specificity, detection limit, quantitation limit, linearity, range, and robustness. These characteristics are those recommended by the ICH and will be discussed first. 

Reliable quality control in the field of pharmaceutical analysis is based on the use of valid analytical methods. For this reason, any analytical procedures proposed for a particular active pharmaceutical ingredient and its corresponding dosage forms shonld be validated to demonstrate that they are scientifically sonnd nnder the experimental conditions intended to be used. Since dissolntion data reflect drng prod-net stability and quality, the HPLC method used in snch tests shonld be validated in terms of accuracy, precision, sensitivity, specificity, rngged-ness, and robustness as per ICH guidelines. 

ISO defines validation as Conformation by examination and provision of objective evidence that the particular requirements for a specified intended use are fulfilled. This is decided by using a number of performance characteristics. These are specificity, linearity, range, accuracy, precision, detection limit (DL), quantitation limit (QL), and robusmess. System suitability testing (SST) is an integral part of many analytical procedures. Definitions of these terms based on the recommendations of the ICH Guideline Q2 (Rl) are given in Table... 

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