Multielemental speciation analysis of organometallic compounds of mercury, lead and tin in natural water samples by headspace-solid phase microextraction followed by gas chromatography–mass spectrometry

The development of a simple and rapid multielemental speciation method is described with the ultimate goal to simultaneously determine various organometallic compounds of mercury, lead and tin (inorganic mercury, methylmercury, trimethyllead, triethyllead, monobutyl-, dibutyl- and tributyltin) in natural water samples. The analytical method consists on the ethylation with NaBEt4, simultaneous headspace-solid phase microextraction (HS-SPME) of the derivatives and final gas chromatographic-mass spectrometric (GC–MS) analysis. After optimization of important process parameters, like SPME fiber coating, extraction time and extraction temperature, the analytical characteristics were evaluated. Detection limits in the low ng l−1 level, linearity over three orders of magnitude and repeatability in the range of 3–20% were achieved for all compounds under study. The accuracy of the method in terms of average percentage recovery of the compounds in spiked river water and seawater samples was better than 90%. Finally, application of the proposed method to real natural aqueous samples enabled the simultaneous determination of all the compounds under study in seawater samples obtained from the marina area of Gijón (Asturias, Spain).