Measurement uncertainty: Approaches to the evaluation of uncertainties associated with recovery†

A number of approaches for evaluating recovery and its contribution to uncertainty budgets for analytical methods are considered in detail. The recovery, R, for a particular sample is considered as comprising three elements, m, Rs and Rrep. These relate to the recovery for the method; the effect of sample matrix and/or analyte concentration on recovery; and how well the behaviour of spiked samples represents that of test samples. The uncertainty associated with R, u(R), will have contributions from u(m), u(Rs) and u(Rrep). The evaluation of these components depends on the method scope and the availability, or otherwise, of representative certified reference materials. Procedures for evaluating these parameters are considered and illustrated with worked examples. Techniques discussed include the use of certified reference materials and spiking studies, and the use of extraction profiling to predict recoveries. All the approaches discussed evaluate the recovery and its uncertainty for the analytical method as a whole. It is concluded that this is a useful approach as it reduces the amount of experimental work required. In addition, most of the required data are frequently available from method validation studies.