Chemical signatures of TNT-filled land mines

The equilibrium headspace above several military-grade explosives was sampled using solid phase microextraction fibers and the sorbed analytes determined using gas chromatography with an electron capture detector (GC-ECD). The major vapors detected were the various isomers of dinitrotoluene (DNTs), dinitrobenzene (DNBs), and trinitrotoluene (TNTs), with 2,4-DNT and 1,3-DNB often predominating. Although 2,4,6-TNT made up from 50 to 99% of the solid explosive, it was only a minor component of the equilibrium vapor. The flux of chemical signatures from intact land mines is thought to originate from surface contamination and evolution of vapors via cracks in the casing and permeation through polymeric materials. The levels of external contamination were determined on a series of four types of Yugoslavian land mines (PMA-1A, PMA2, TMA5 and TMM1). The flux into air as a function of temperature was determined by placing several of these mines in Tedlar bags and measuring the mass accumulation on the walls of the bags after equilibrating the mine at one of five temperatures. TNT was a major component of the surface contamination on these mines, yet it accounted for less than 10% of the flux for the three plastic-cased mines, and about 33% from the metal antitank mine (TMM1). Either 2,4-DNT or 1,3-DNB produced the largest vapor flux from these four types of land mines. The environmental stability of the most important land mine signature chemicals was determined as a function of temperature by fortifying soils with low aqueous concentrations of a suite of these compounds and analyzing the remaining concentrations after various exposure times. The kinetics of loss was not of first order in analyte concentration, indicating that half-life is concentration dependent. At 23 degrees C, the half life of 2,4,6-TNT, with an initial concentration of about 0.5 mg kg(-1), was found to be only about 1 day. Under identical conditions, the half-life of 2,4-DNT was about 25 days. A research minefield was established and a number of these same four mine types were buried. Soil samples were collected around several of these mines at several time periods after burial and the concentration of signature chemicals determined by acetonitrile extraction and GC-ECD analysis. Relatively high concentrations of 2,4,6-TNT and 2,4-DNT were found to have accumulated beneath a TMA5 antitank mine, with lower concentrations in the soil layers between the mine and the surface. Signatures were distributed very heterogeneously in surface soils, and concentrations were very low (low mug kg(-1) range). Lower, but detectable, concentrations of signatures were detectable irregularly in soils near the PMA-1A mines in contrast to the TMA5 mines. Concentrations of signature chemicals were generally below detection limits (<1 mug kg(-1)) near the TMM1 and PMA-2 mines, even 8 months after burial.