Solid-phase microextraction combined with gas chromatography and atomic emission detection for the determination of cyclopentadienylmanganese tricarbonyl and (methylcyclopentadienyl)manganese tricarbonyl in soils and seawaters

A method based on solid-phase microextraction with capillary gas chromatography and microwave-induced plasma atomic emission detection (SPME-GC-MIP-AED) for the determination of cyclopentadienylmanganese tricarbonyl (CMT) and its methyl derivative, (methylcyclopentadienyl)manganese tricarbonyl (MMT) in seawaters and soils was optimized and evaluated. The solvent-free preconcentration step was carried out in the headspace (HS) mode. Element-specific detection and quantification was carried out by monitoring the manganese (259 nm) emission line. A matrix effect was found for the soil samples investigated, so that standard additions were required for their quantification. On the other hand seawaters were analyzed by applying direct calibration against aqueous standards. Detection limits of 13 and 15 pg Mn L−1 were obtained for CMT and MMT, respectively, in seawaters, and 0.62 and 0.65 pg Mn g−1, respectively, for the soil samples. The method permitted recoveries of 76–113%, depending on the compound and the sample analyzed, confirming the reliability of the procedure and its suitability for routine monitoring purposes.