Use of solid-phase microextraction/gas chromatography–electron capture detection for the determination of energetic chemicals in marine samples

Abstract

Gas chromatography with electron capture detection (GC–ECD) is a highly explosive–sensitive analytical technique. However, its application to the analysis of sediment extracts is hampered by the presence of numerous endogenous interferences. In the present study, solid-phase microextraction (SPME) was used both as a purification technique for sediment extracts and as an extraction technique for water samples prior to analysis by GC–ECD. SPME/GC–ECD coupling was optimized and applied to the trace analysis of nine explosives including nitroaromatics and RDX in real seawater and marine sediment samples. Addition of a high concentration of salt (30%, w/v) in the aqueous medium and use of a carbowax/divinylbenzene (CW/DVB) coating led to optimal extraction efficiencies. Method detection limits (MDLs) ranged from 0.05 to 0.81 μg/L in water and from 1 to 9 μg/kg in dry sediment. Except for RDX, spike recoveries in seawater were satisfactory (89–147%) when samples were fortified at 2 μg/L of each analyte. Spike recoveries from dry sediment fortified at 10 μg/kg of each analyte gave lower recoveries but these could also be due to degradation in the matrix. With a smaller volume of aqueous sample required compared to solid-phase extraction (SPE), SPME is an attractive method for the analysis of limited volumes of sediment pore-water. Moreover, the use of SPME eliminated interferences present in sediment extracts thus allowing the detection of the target analytes that were otherwise difficult to detect by direct injection.