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

Abstract

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 NaBEt4 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).