Determination of total selenium and 77Se in isotopically enriched human samples by ICP-dynamic reaction cell-MS

Abstract

This paper describes an analytical method for the simultaneous quantitative determination of total selenium (Se) and 77Se in isotopically enriched human plasma, urine and faeces by inductively coupled plasma-dynamic reaction cell-mass spectrometry (ICP-DRC-MS). The samples originated from a human study in which a single dose of 327 µg 77Se (99.3% pure) had been given as intrinsically 77Se-labelled yeast, following administration for six weeks of 300 µg d−1 of selenium also as selenised yeast with natural isotope abundance. Prior to analysis, the plasma and urine samples and the digested faecal samples were diluted using an aqueous diluent containing 0.5% Triton X-100, 2% nitric acid and 3% methanol. Selenium was detected as 76Se, 77Se and 80Se by ICP-DRC-MS. Selenium originating from the natural isotope abundance yeast and other selenium sources from the diet was determined as 80Se, which was unaffected by the isotope enrichment. The degree of enrichment of 77Se was estimated from the measured 77Se signal intensity (natural abundance plus enrichment) minus the natural abundance of this isotope, which was calculated from measurement of 76Se. Quantification of the enriched amount of selenium 77Se was carried out against standard additions calibration curves (natural isotope abundance) by correcting the slope of the 77Se calibration curve according to the 99.3% abundance of this isotope in the enriched fraction. The limits of detection for selenium with natural abundance were 0.1 µg l−1, 0.2 µg l−1 and 6 µg kg−1 and the minimum detectable increase in 77Se was 0.38 µg l−1, 0.58 µg l−1 and 15 µg kg−1 (corresponding to 0.21%, 0.63% and 0.61% of the mean total selenium concentrations in this study) in plasma, urine and faeces, respectively. The accuracy was controlled by analysis of the reference materials Seronorm Serum and BCR 185 Bovine Liver.