Uncertainty of sampling in chemical analysis

Abstract

Uncertainty of sampling is the contribution from sampling errors to the combined uncertainty associated with an analytical measurement when the measurand is the concentration of the analyte in the ‘target’, the total bulk of material that the sample is meant to represent. Of the errors considered to contribute to uncertainty, random errors of sampling, characterised by precision, are much more accessible to investigation than those due to bias. Where an approximation to random sampling can be achieved, realistic precisions can normally be estimated. In some instances reproducibility precision is significantly greater than repeatability precision, and the contribution of between-sampler variations to sampling uncertainty must be acknowledged. However, the collaborative trial of a sampling method is an expensive and difficult exercise to execute. A system of internal quality control for routine sampling can be introduced. Fitness for purpose has been defined in terms of the required combined uncertainty of sampling and analysis.