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

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 mug/L in water and from I to 9 mug/kg in dry sediment. Except for RDX, spike recoveries in seawater were satisfactory (89-147%) when samples were fortified at 2 mug/L of each analyte. Spike recoveries from dry sediment fortified at 10 mug/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. (C) 2005 Elsevier B.V. All rights reserved.