Using speciated isotope dilution with GC-inductively coupled plasma MS to determine and unravel the artificial formation of monomethylmercury in certified reference sediments.

Speciated isotope-dilution mass spectrometry (SID-MS) is claimed to be an absolute method; however, it has been found to be affected by artifact monomethylmercury (MMHg) formation in sediments. The determination of MMHg in sediments was carried out by SID-MS after open-focused microwave extraction. The extracted mercury species were then ethylated and separated by capillary gas chromatography (CGC). Isotope ratios (peak area ratios at different masses) were measured by on-line ICP-MS detection of the CGC-separated compounds. Reproducibility of 202Hg/201Hg isotope ratio measurements were 0.60% for MeEtHg and 0.69% for Et2Hg; for 202Hg/199Hg, 0.43 and 0.46%, respectively, were determined. The absolute detection limits for CGC-ICPMS measurements were better than 26 fg for 202Hg, 20 fg for 201Hg, and 24 fg for 199Hg. For the direct determination of MMHg in sediment reference materials (CRM 580, IAEA 356, and IAEA 405), higher values than the certified were always found. Systematic experiments were carried out to localize the sources of the unintentional abiotic methylmercury formation during analysis. Different spiking and derivatization procedures (either ethylation, propylation, or derivatization by Grignard reagents) were tested. In addition, isotopically enriched inorganic mercury was spiked. The amount of inorganic mercury initially present in the sample was found to be the critical factor that should be known and carefully controlled. A simple solvent extraction technique involving no critical cleanup steps was applied in order to reduce high Hg2+ amounts. The method was applied to the determination of MMHg in sediment reference material IAEA-405 with satisfactory results after organic solvent extraction. The limitations of applicability of the proposed method are evaluated as related to inorganic mercury, organic carbon, and sulfur contents. The results obtained confirmed that available sediment reference materials are adequate to achieve traceable mercury speciation analysis and to detect potential sources of MMHg artifact formation.