Determination of very low levels of dissolved mercury(II) and methylmercury in river waters by continuous flow with on-line UV decomposition and cold-vapor atomic fluorescence spectrometry after pre-concentration on a silica gel-2-mercaptobenzimidazol sorbent.

A new, simple and sensitive method for the simultaneous determination of mercury(II) and methylmercury chloride at sub-ng l(-1) levels in river waters is described. Inorganic and organic mercury were preconcentrated from fresh water samples simultaneously on a laboratory-made column containing 2-mercaptobenzimidazol loaded on silica gel and then quantitatively eluted with 0.05 M KCN solution and 2.0 M HCl to desorp inorganic and methylmercury species, respectively. After irradiation with an intensive UV source, MeHg(+) was decomposed and mercury vapours were generated from inorganic and organic mercury using an acidic SnCl(2) solution in a continuous flow system and were subsequently determined with a cold vapour atomic fluorescence (CV-AFS) spectrometer. Detection limits (3sigma) were 0.07 and 0.05 ng l(-1) (as Hg) for mercury(II) chloride and methylmercury chloride, respectively. Relative standard deviations of method (%R.S.D.) were 8.8 and 10 for inorganic and organomercuric species in the river water, respectively. The analysis of real samples, taken from different rivers, showed that inorganic mercury levels ranged from 4.0+/-0.6 to 12+/-1 ng l(-1) (as Hg and 95% confidence limit) and methylmercury levels at 0.2+/-0.02 ng l(-1)(as Hg).