Estimation of measurement uncertainty arising from manual sampling of fuels

Sampling is an important part of any measurement process and is therefore recognized as an important contributor to the measurement uncertainty. A reliable estimation of the uncertainty arising from sampling of fuels leads to a better control of risks associated with decisions concerning whether product specifications are met or not. The present work describes and compares the results of three empirical statistical methodologies (classical ANOVA, robust ANOVA and range statistics) using data from a balanced experimental design, which includes duplicate samples analyzed in duplicate from 104 sampling targets (petroleum retail stations). These methodologies are used for the estimation of the uncertainty arising from the manual sampling of fuel (automotive diesel) and the subsequent sulfur mass content determination. The results of the three methodologies statistically differ, with the expanded uncertainty of sampling being in the range of 0.34–0.40 mg kg−1, while the relative expanded uncertainty lying in the range of 4.8–5.1%, depending on the methodology used. The estimation of robust ANOVA (sampling expanded uncertainty of 0.34 mg kg−1 or 4.8% in relative terms) is considered more reliable, because of the presence of outliers within the 104 datasets used for the calculations. Robust ANOVA, in contrast to classical ANOVA and range statistics, accommodates outlying values, lessening their effects on the produced estimates. The results of this work also show that, in the case of manual sampling of fuels, the main contributor to the whole measurement uncertainty is the analytical measurement uncertainty, with the sampling uncertainty accounting only for the 29% of the total measurement uncertainty.