Methylmercury determination in freshwater biota and sediments: Static headspace GC-MS compared to direct mercury analyzer

We developed and compared two analytical methods for determination of MeHg in freshwater biota and sediments, by: I) simplified static headspace GC-MS using internal standard (IS) isotope dilution quantification, after microwave acid digestion and aqueous phase NaBEt(4) ethylation; II) Automated Mercury Analyzer, after double toluene extraction followed by back-extraction with L-cystein. The performance was evaluated by analysis of certified reference materials. For biota, mean recovery was 100 ± 2% and relative standard deviation (RSD) ≤ 6.8% for method I, and mean recovery was 98 ± 7% and RSD ≤13% for method II. For sediments, recovery of 94.5% and RSD of 8.8% were obtained with method I, and recovery of 90.3% and RSD of 9.4% with method II. Limits of detection (LOD) were 0.7 µg kg(−1) and 6 µg kg(−1), respectively. Both techniques were tested for MeHg analysis in freshwater invertebrates, fish and sediments, covering a large range of MeHg values (1.9–670 µg kg(−1) d.w.). • Both protocols proved to be suitable for MeHg analysis in complex environmental matrices, even if, for method II, interferences in the extraction phase and limited sensitivity may hinder sediment analysis. • Passing-Bablock regression revealed a slight disproportion between methods, with line slope = 1.058 (95% CI ranging from 1.001 to 1.090).