 Analytical sampling uncertainty

Analytical sampling uncertainty is the contribution to measurement uncertainty arising when collected material is used to infer a property of a specified sampling target. The target might be a bulk lot or a defined location and time interval. Its composition need not equal that of one convenient portion. Sampling and physical preparation therefore belong in the measurement model when the measurand concerns the larger target.^[ref]

A duplicated experiment can separate two random components. Within each target, collect two independent samples by the stated protocol, prepare them separately, and analyse each twice. For a simple model,where $i=1,2$ labels collection and $j=1,2$ labels analysis; all random terms are centered and independent except for the shared $S_i$ within a sample. The within-sample difference has variance $2{\sigma }_a^2$. The difference between the two sample means has variance $2{\sigma }_s^2+{\sigma }_a^2$. Repeating this design across targets supports estimation of both components; different target means cancel in each within-target difference.^[ref]

For original stipulated difference standard deviations2and5milligrams per kilogram, respectively,in squared concentration units. One analysis on one sample has combined standard deviation $\sqrt{13.5}\approx 3.67$milligrams per kilogram. Averaging two analyses of that same sample gives $\sqrt{11.5+2/2}\approx 3.54$; averaging one analysis from each of two independent samples gives $\sqrt{(11.5+2)/2}\approx 2.60$. More laboratory replication and more independent collection address different contributions.

A collaborative wheat-and-coffee trial varied the sampler as well as the collected material. Its contrasting reproducibility and repeatability findings show why the uncertainty depends on which collection conditions are allowed to vary.^[ref]

Duplicate sampling with one sampler and protocol does not establish absence of a shared sampling bias. Reference comparisons, alternative protocols or inter-organisational trials can test additional effects. Common preparation losses or measurement calibration errors also require covariance terms beyond the independent model.