A Reliable Method to Determine Monomethylmercury and Monoethylmercury Simultaneously in Aqueous Samples by GC–CVAFS After Distillation

A reliable method for simultaneous determination of monomethylmercury (MeHg) and monoethylmercury (EtHg) in water by gas chromatography with cold vapor atomic fluorescence spectrometry was developed and validated. The experimental conditions, including derivatisation pH, distillation, and complexing agents, were optimized in detail. The absolute detection limits (3σ) were 0.007 ng/L as Hg for MeHg and 0.004 ng/L as Hg for EtHg. The relative standard deviation values (n = 6) for 0.1 ng/L of MeHg and EtHg were 2.7 and 2.1%, 1.0 ng/L of MeHg and EtHg were 6.0 and 6.9%, 4.4 ng/L of MeHg and EtHg were 2.8 and 2.7%, respectively. In addition, five different water samples were analyzed, including river water (RW), effluent wastewater (EW), seawater (SW), industrial wastewater (IW), underground water (UW), and the spiked recoveries of MeHg, were all greater than 85%, whereas EtHg was 86.0% in RW, 83.0% in EW, 87.0% in UW, 82.6% in SW, and 80% in IW. Formation of artefact MeHg and EtHg was studied during distillation. The level of artefact MeHg formed by methylation of Hg(II) during distillation varies from ~ 0.002 to 0.009% for river water and from ~ 0.002 to 0.004% for effluent wastewater, ethylation of Hg(II) was not observed. The method was validated for a variety of water sources with Hg(II) concentrations under 440 ng/L.