Estimation of the uncertainty associated with the standard addition methodology when a matrix effect is detected

If a matrix effect is detected during the validation stage of an analytical method, the standard addition methodology must be applied. To reach a good estimation of the uncertainty associated with the determination, an adequate identification and evaluation of each uncertainty source should be done. As an example to illustrate how to calculate the uncertainty in this case, the simultaneous determination of V(V) and Mo(VI) at trace levels after precolumn chelation and extraction with N-benzoyl-N-phenylhydroxylamine, has been selected. The final results show that the main contributions to the relative overall uncertainty are those closely related with the chemical aspects of the method, i.e. liquid–liquid extraction and standard addition calibration.