Determination of cadmium in biological and environmental materials by isotope dilution inductively coupled plasma mass spectrometry: effect of flow sample introduction methods

Experimental parameters governing the instrumental precision and accuracy for isotope ratio measurements of cadmium in ICP-MS, including sampling time, mass bias, detector dead-time and spectroscopic interferences, were first characterised. The precision achieved for the isotope ratio determination of Cd was around 0.2% (RSD for n = 5) both for 111 : 112 and 111 : 114 ratios. Two alternative flow approaches for the determination of ultratrace concentrations of cadmium by isotope dilution (ID) were explored and compared with the more conventional ID methodology: first, on-line mixing of the sample solution with the spike solution just before the ICP-MS nebuliser using a peristaltic pump and, second, the generation of volatile cadmium species using sodium tetraethylborate by merging zones flow injection ICP-MS. The three approaches were successfully applied to the determination of ultratrace levels of cadmium in biological and environmental certified reference materials (NIST RM 2670 Freeze-Dried Urine, IAEA H-8 Horse Kidney, BCR TP-25 Lichens, PACS-1 Marine Sediment and SLRS-3 Riverine Water). The on-line ID method proved to be the most convenient for the determination of cadmium in such samples because it is fast, provides similar results to those of conventional ID and requires less sample preparation.