Measurements accuracy and precision

A significant increase in the measuring precision and accuracy can sometimes be attained by differential measurement with two ISEs. Two principal approaches can be taken ... 

The magnitude of the uncertainty associated with a measurement should always be evaluated even if method development is able to generate the best, error-free standard curve possible in order to obtain the best, error-free concentration values for the unknown. Precision and accuracy values define the compromise between the demand for certainty in reported results and the inherent uncertainty in bioanalytical measurement. Precision and Accuracy are the most important parameters used to set the performance standards of bioanalytical methods. They define if the zone of uncertainty connected with the data produced by the method is or is not acceptable for the specific task [13,21]. 

Compare performance against industry requirements to assess outcome and opportunity Improve measurement precision and accuracy Field test for reliability and lifetime... 

A.B. Thompson, E.M. Sevick-Muracka, Near-infrared fluorescence contrast-enhanced imaging with intensified charge-coupled device homodyne detection measurement precision and accuracy, J. Biomed. Opt. 8, 111-120 (2003)... 

The coupling of sensors with flow injection analysis (FIA) is already a very popular option. The flow regime offers important advantages over discrete manual measurements that include (1) Sample preparation processes such as reagent mixing, selectivity enhancement (e.g., removal of large molecular mass interferents such as protein by dialysis in clinical assays), and solvent extraction can all be carried out online. The improved sample preparation and more reproducible sample delivery result in improved measurement precision and accuracy. Drift is less of a problem as measurements are made of peak heights relative to a baseline. (2) Improved sensor lifetime in flow analysis, the sensor may be exposed to the sample for only a short period of time, and maintained in a friendlier matrix between measurements that can help counteract or delay the deleterious effects of the sample. (3) Automation the entire analysis can be... 

A second viewpoint is often heard and was epitomized by Richtmyer s phrase "the romance of the next decimal place" [2]. I don t wish to trivialize this message but it has certain limitations. The positive content is that improved measurement precision and accuracy have often led to new discoveries and are likely to do so in the future. Examples are legion extending from early astrometry through the discovery of the rare gases and surely into our present decade. A problem with this perspective is that it offers little in the way of guidance as to what directions one should emphasize. 

A similar situation arises regarding the intensity measurement precision and accuracy of calibration. Again from the S/N point of view we can often measure spectral intensities to 1 part in 10. However the linearity of the response between 0 and 100% transmission is by no means known to this precision. There are many factors affecting the accuracy of intensity measurement. A fundamental problem relates to the geometrical optical properties of the sample the most severe... 

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. 

Orifice. Orifice viscometers, also called efflux or cup viscometers, are commonly used to measure and control flow properties in the manufacture, processing, and appHcation of inks, paints, adhesives, and lubricating oils. Their design answered the need for simple, easy-to-operate viscometers in areas where precision and accuracy are not particularly important. In these situations knowledge of a tme viscosity is uimecessary, and the efflux time of a fixed volume of Hquid is a sufficient indication of the fluidity of the material. Examples of orifice viscometers include the Ford, Zahn, and Shell cups used for paints and inks and the Saybolt Universal and Furol instmments used for oils (Table 5). 

If the random errors are higher than can be tolerated to meet the goals of the test, the errors can be compensated for with rephcate measurements and a commensurate increase in the laboratory resources. Measurement bias can be identified through submission and analysis of known samples. Establishing and justifying the precision and accuracy reqrtired by the laboratory is a necessary part of estabhshing confidence. 

To find the best a priori conditions of analysis, the equilibrium analysis, based on material balances and all physicochemical knowledge involved with an electrolytic system, has been done with use of iterative computer programs. The effects resulting from (a) a buffer chosen, (b) its concentration and (c) complexing properties, (d) pH value established were considered in simulated and experimental titrations. Further effects tested were tolerances in (e) volumes of titrants added in aliquots, (f) pre-assumed pH values on precision and accuracy of concentration measured from intersection of two segments obtained in such titrations. 

ICPMS is uniquely able to borrow a quantitation technique from molecular mass spectrometry. Use of the isotope dilution technique involves the addition of a spike having a different isotope ratio to the sample, which has a known isotope ratio. This is usefiil for determining the concentration of an element in a sample that must undergo some preparation before analysis, or for measuring an element with high precision and accuracy. ... 

In order to answer this question, we should not consider the chromatographic resolution in isolation but in conjunction with the selectivity of the detector. If the detector is not selective, i.e. we cannot isolate the signal resulting from the analyte from those representing the other compounds present, we must rely on the chromatographic resolution to provide a signal which is measurable with sufficient precision and accuracy. If, however, the detector has sufficient selectivity... 

The precision and accuracy of a quantitative measurement are of great importance. 

If we consider the electrospray spectrum of horse heart myoglobin shown pre-vionsly (see Figure 4.11), the information given in Table 4.1 may be obtained by application of the above equations. The precision and accuracy of these measurements are also shown in this table. 

Definition and Uses of Standards. In the context of this paper, the term "standard" denotes a well-characterized material for which a physical parameter or concentration of chemical constituent has been determined with a known precision and accuracy. These standards can be used to check or determine (a) instrumental parameters such as wavelength accuracy, detection-system spectral responsivity, and stability (b) the instrument response to specific fluorescent species and (c) the accuracy of measurements made by specific Instruments or measurement procedures (assess whether the analytical measurement process is in statistical control and whether it exhibits bias). Once the luminescence instrumentation has been calibrated, it can be used to measure the luminescence characteristics of chemical systems, including corrected excitation and emission spectra, quantum yields, decay times, emission anisotropies, energy transfer, and, with appropriate standards, the concentrations of chemical constituents in complex S2unples. 

Functions of Standards. Fluorescent standards can be used for three basic functions calibration, standardization, and measurement method assessment. In calibration, the standard is used to check or calibrate Instrument characteristics and perturbations on true spectra. For standardization, standards are used to determine the function that relates chemical concentration to Instrument response. This latter use has been expanded from pure materials to quite complex standards that are carried through the total chemical measurement process (10). These more complex standards are now used to assess the precision and accuracy of measurement procedures. 

Our goals in designing the immersion testing system were (i) to emulate or improve upon operations as specified in the manual immersion test method, (ii) to increase sample throughput, (iii) to improve the precision and accuracy of measurements, (iv) to establish procedures for testing materials in hazardous liquids, and (v) to provide sufficient flexibility to handle different types of specimens and enable future expansion of operations. 

Currently, nutrient analytical methods development often utilizes the method of standard additions as an intrinsic aspect of the development process. Essentially, the analyte to be measured exists in the matrix to which an identical known pure standard is added. The spiked and non-spiked matrix is extracted and analysed for the nutrient of interest. By spiking at increasing levels the researcher can establish, to some degree of certainty, the recovery and linearity of the standard additions. One can also evaluate data to determine reproducibility, precision, and accuracy. Unfortunately, the method of standard additions does not allow the evaluation of the method at nutrient concentrations less than 100 % of the endogenous level. 

One of the limitations of the portable field survey instruments in the measurement of americium is that their quantitative accuracy depends on how well the lateral and vertical distribution of americium in the soil compares with the calibration parameters used. These methods can provide a rapid assessment of americium levels on or below surfaces in a particular environment however, laboratory-based analyses of samples procured from these environmental surfaces must be performed in order to ensure accurate quantification of americium (and other radionuclides). This is due, in part, to the strong self absorption of the 59.5 keV gamma-ray by environmental media, such as soil. Consequently, the uncertainty in the depth distribution of americium and the density of the environmental media may contribute to a >30% error in the field survey measurements. Currently, refinements in calibration strategies are being developed to improve both the precision and accuracy (10%) of gamma-ray spectroscopy measurements of americium within contaminated soils (Fong and Alvarez 1997). 

The first applications of this technique [99] were directed to developing a more sensitive assessment of lubricant efficiency than that offered by the traditional coefficient of lubrication , or R-value (i.e., FL FA ratio). Since then, its use has been extended to provide predictive information on formulation performance [100,101]. Lammens et al. [102] have stressed the importance of ensuring precision and accuracy in such measurements for correct interpretation of the data so produced. 

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. 

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