Chemometrics in f-element speciation: a metrological challenge?

The UV–Vis spectra of the f-elements, especially the lanthanides, are known for their rather sharp absorption bands showing systematic and reproducible changes upon coordination with suitable ligands. These absorption bands have been used as indicators allowing interpretation of the processes in solution. Modern absorption spectrometers in combination with digital recording of the spectra allow a precise collection of a large number of absorptions for many samples. The number of absorption thus collected easily amounts to several thousands of individual data. Chemometric techniques, especially factor analysis, are occasionally used to extract information from these data sets on basis of Bouguer–Lambert–Beer law. Recent studies indicate the sensitivity of parameter values obtained from uncritical use of chemometric techniques to various influence and nuisance factors. On the basis of selected examples, the effects of parameter correlations, residual correlations, and measurement uncertainty introduced by volume operations are demonstrated. Using the ISO Guide to the Expression of Uncertainty as a convention for assessing measurement uncertainty, formation constants lg K derived from UV–Vis spectra of f-elements should be associated with a measurement uncertainty u of at least u = 0.15 ( k = 1).