Assessment of quality performance parameters for straight line calibration curves related to the spread of the abscissa values around their mean

In validation of quantitative analysis methods, knowledge of the response function is essential as it describes, within the range of application, the existing relationship between the response (the measurement signal) and the concentration or quantity of the analyte in the sample. The most common response function used is obtained by simple linear regression, estimating the regression parameters slope and intercept by the least squares method as general fitting method. The assumption in this fitting is that the response variance is a constant, whatever the concentrations within the range examined. The straight calibration line may perform unacceptably due to the presence of outliers or unexpected curvature of the line. Checking the suitability of calibration lines might be performed by calculation of a well-defined quality coefficient based on a constant standard deviation. The concentration value for a test sample calculated by interpolation from the least squares line is of little value unless it is accompanied by an estimate of its random variation expressed by a confidence interval. This confidence interval results from the uncertainty in the measurement signal, combined with the confidence interval for the regression line at that measurement signal and is characterized by a standard deviation s(x0) calculated by an approximate equation. This approximate equation is only valid when the mathematical function, calculating a characteristic value g from specific regression line parameters as the slope, the standard error of the estimate and the spread of the abscissa values around their mean, is below a critical value as described in literature. It is mathematically demonstrated that with respect to this critical limit value for g, the proposed value for the quality coefficient applied as a suitability check for the linear regression line as calibration function, depends only on the number of calibration points and the spread of the abscissa values around their mean. (c) 2006 Published by Elsevier B.V.