Determination of Mn(II) and Mn(VII) in beverage samples using magnetic dispersive micro-solid phase extraction coupled with solidified floating organic drop microextraction followed by graphite furnace atomic absorption spectrometry.

Magnetic dispersive micro-solid phase extraction (MDMSPE) was coupled with solidified floating organic drop microextraction (SFODME) for direct separation and preconcentration of Mn(II) and Mn(VII) before graphite furnace atomic absorption spectrometry determination. MDMSPE involved use of magnetic ZnFeO nanotubes for adsorbing Mn(VII). Sorbent was isolated from aqueous phase by an external magnet. Mn(II) in upper solution from MDMSPE was further enriched by SFODME. This method avoids tedious pre-oxidation/pre-reduction operation and time-consuming centrifugation/filtration step. An enrichment factor of 200-fold was obtained. Detection limits of this method were 0.005 and 0.007 ng mL for Mn(II) and Mn(VII) with relative standard deviations of 4.0% and 4.8% (n = 9), respectively. This method was successfully used for detection of Mn(II) and Mn(VII) in tap water, ice tea, energy drink, mineral water, sprite drink and carbonated drink. A certified reference material of water sample was analyzed with satisfactory results. Recoveries of spike experiments ranged from 92.5 to 106%.