Evaluation of different approaches to applying the standard additions calibration method

The extrapolation approach, traditionally used with standard additions (SA), is compared with the alternative strategies of interpolation, reversed-axis, and normalization. The interpolation approach is based on employing twice the analytical signal recorded for the sample (y_sam) to determine an unknown analyte concentration. In the reversed-axis strategy, x- and y-axes are swapped when building the SA calibration plot to facilitate uncertainty estimation. A new strategy, based on signal normalization using y_sam, is also described and compared to the other approaches. Results from 3 instrumental methods, 396 sample replicates, 16 analytes, and 2 certified reference materials are included in this study. For most applications, all four SA approaches provide statistically similar trueness and precision. However, extrapolation and reversed-axis provide more consistent values (within narrower ranges) than the other strategies when employing inductively coupled plasma optical emission spectrometry (ICP OES). On the other hand, normalization provides better trueness for the less robust method of microwave-induced plasma OES (MIP OES), as it is capable of minimizing systematic errors associated with different points of the calibration curve. Normalization is particularly useful for quickly processing data, without the need for inspecting each individual calibration plot to identify outlying points. Reversed-axis and normalization are the most adequate approaches for SA applications involving MIP OES and ICP-based methods. In addition to providing similar accuracies to the traditional extrapolation approach, these strategies present the advantage of a simple uncertainty estimation, which can be easily calculated using commonly available software such as Microsoft Excel and R.