Determination of total urinary mercury by on‐line sample microwave digestion followed by flow injection cold vapour inductively coupled plasma mass spectrometry or atomic absorption spectrometry

The total mercury content in urine was determined by inductively coupled plasma mass spectrometry with the so-called cold vapour method after on-line oxidative treatment of the sample in a microwave oven (FI-MW-CV-ICPMS). Use of a KBr/KBrO3 mixture, microwave digestion, and the final oxidation with KMnO4, assure the complete recovery of the organic forms of Hg which would be difficult to determine otherwise if using only the CV-ICPMS apparatus. Quantitative recoveries were obtained for phenyl Hg chloride (PMC), dimethyl Hg (DMM), Hg acetate (MA) and methyl Hg chloride (MMC). Use of automatic flow injection microwave systems (FI-MW) for sample treatment reduces environmental contamination and allows detection limits suitable for the determination of reference values. Since no certified reference materials were commercially available in the concentration ranges of interest, the accuracy of the proposed procedure has been assessed by analysing a series of urine samples with two independent techniques, ICP-MS and AAS. When using the FI-MW-CV-ICP-MS technique, the detection limit was assessed at 0.03µg/L Hg, while with FI-MW-CV-AAS it was 0.2µg/L Hg. The precision of the method was less than 2–3% for FI-MW-CV-ICP-MS and about 3–5% for FI-MV-CV-AAS at concentrations below 1µg/L Hg. These results show that ICP-MS can be considered as a “reference technique” for the determination of total urinary Hg at very low concentrations, such as are present in non-exposed subjects. Copyright © 2002 John Wiley & Sons, Ltd.