Development of a novel and robust microprecipitation approach using cetyltrimethyl ammonium bromide (CTAB) for preconcentration and speciation of mercury in waters prior to CVAAS determination

A novel and simple microprecipitation method was developed for the preconcentration of ultra-trace quantities of inorganic and methyl mercury species (iHg and MeHg) prior to their determination by cold vapour atomic absorption spectrometry (CVAAS). This method is based on the formation of anionic complexes of Hg²⁺ with KI followed by ion-associate complex with cetyltrimethyl ammonium bromide (CTAB) that forms a fluffy precipitate in perchloric acid medium. As a result, a fluffy coagulated mass separates and collects at the top of the liquid surface with clear phase separation without need of cooling or heating or centrifugation. The ion-association complex of iHg was then extracted into surfactant-rich phase (top layer) of CTAB-perchlorate precipitate while the uncomplexed MeHg remained in the aqueous phase (bottom layer). This condition also facilitates the removal of aqueous phase by simply draining out. The fluffy mass formed was dissolved in a mixture of HNO₃ and HCl which was subsequently treated with chloroform to separate the surfactant from the mixture. Then the aqueous phase containing the preconcentrated iHg was analysed for mercury by CVAAS. Key factors such as sample pH, concentration of KI and CTAB that affect the performance of the proposed microprecipitation method were thoroughly investigated. For the determination of total mercury, another fresh aliquot of water was initially adjusted to pH ~ 3.5 with perchloric acid and subjected to oxidation by using modified UV-irradiation set-up and then taken through the microprecipitation procedure. This method allows speciation of mercury with a preconcentration factor of 200 and the limits of detection (LOD) of mercury obtained for CVAAS in conjunction with the present preconcentration method was found to be 2.4 ng L^?1. Average recoveries obtained with the proposed approach were found to be in the range of 96–104% with RSD values < 5%. The interfering effects of various cations and anions were also investigated. The method was successfully applied for the determination of ultra-trace quantities of mercury species in real samples such as bottled water, tap water, lake water and ground waters.