Methylmercury in water samples at the pg/L level by online preconcentration liquid chromatography cold vapor-atomic fluorescence spectrometry

Ultra-traces of methylmercury at the sub-ppt level can be magnified in the foodweb and is of concern. In environmental monitoring a routine robust analytical method is needed to determine methylmercury in water. The development of an analytical method for ultra-trace speciation analysis of methylmercury (MeHg) in water samples is described. The approach is based on HPLC-CV-AFS with on-line preconcentration of water samples up to 200 mL, resulting in a detection limit of 40 pg/L (ppq) for MeHg, expressed as Hg. The unit consists of an optimized preconcentration column filled with a sulfur-based sorption material, on which mercury species are preconcentrated and subsequently eluted, separated and detected via HPLC-CV-AFS (high performance liquid chromatography-cold vapor atomic fluorescence spectrometry). During the method development a type of adsorbate material, the pH dependence, the sample load rate and the carry-over were investigated using breakthrough experiments. The method shows broad pH stability in the range of pH 0 to 7, without the need for buffer addition and shows limited matrix effects so that MeHg is quantitatively recovered from sewage, river and seawater directly in the acidified samples without sample preparation.