Enhanced Detection of Nitroaromatic Explosive Vapors Combining Solid-Phase Extraction-Air Sampling, Supercritical Fluid Extraction, and Large-Volume Injection-GC

Abstract

A complete method for sampling and analyzing of energetic compounds in the atmosphere is described. The method consists of the hyphenation of several techniques: active air sampling using a solid-phase extraction cartridge to collect the analytes, extraction of the sorbed analytes by toluene/methyl tert-butyl ether modified supercritical fluid extraction (SFE), and analysis of the extract by large-volume injection GC-nitrogen/phosphorus detection. The GC system is equipped with a loop-type injection interface with an early solvent vapor exit, a utilizing concurrent solvent evaporation technique. Chemometric approaches, based on a Plackett-Burman screening design and a central composite design for response surface modeling, were used to determine the optimum SFE conditions. The relative standard deviations of the optimized method were determined to be 4.3 to 7.7%, giving raise to method detection limits ranging from 0.06 to 0.36 ng in the sampling cartridge, equivalent to 6.2-36.4 pg/L in the atmosphere, standard sampling volume 10 L. The analytical method was applied to characterize headspace composition above military grade trinitrotoluene (TNT). Results confirm that 2,4-dinitrotoluene (DNT) and 1,3-dinitrobenzene (DNB) constitute the largest vapor flux, but TNT, 2,6-DNT, and trinitrobenzene TNB were also consistently detected in all the samples.