Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS

The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO3/H2O2 microwave digestion. The thallium isotope amount ratio (n(205Tl)/n(203Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n(206Pb)/n(208Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study ''lead in wine'' organised by the CCQM (Comite Consultatif pour la Quantite de Matiere, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=k x uc, k=2) The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R206,B of the blend between the enriched spike and the sample. (orig.)