ANALYSIS OF NITROAROMATICS AND NITRAMINES IN AMMUNITION WASTE-WATER AND IN AQUEOUS SAMPLES FROM FORMER AMMUNITION PLANTS AND OTHER MILITARY SITES

Waste water from ammunition production sites and aqueous samples (ground and Surface water) on or near former military sites on which explosives were produced or filled, e.g. into shells, may be contaminated by the original explosives-mainly nitrotoluenes (such as dinitrotoluenes, trinitrotoluene (TNT)) and nitramines (such as hexogen (RDX), octogen (HMX), and tetryl) or hexyl, but also by by-products and compounds formed by biodegradation of the explosives such as aminonitrotoluenes, chlorinated nitrobenzenes and nitrophenols. These compounds can be extracted from aqueous samples by liquid/liquid extraction (using dichloromethane or toluene) or by solid phase extraction using C-18 adsorbents with high recoveries (usually greater-than-or-equal-to 85%) provided they contain only one amino group. Nitrotoluenes. chlorinated nitrobenzenes and aminonitrotoluenes (nitrotoluidines) may be determined by gas chronlatography (GC) using selective detectors such as an electron capture detector (ECD), a nitrogen-phosphorus detector (NPD) or a chemiluminescence detector (thermal energy analyzer, TEA). The use of combined gas chromatography/mass spectrometry (GC/MS) under electron impact conditions is even more specific. Detection limits comparable to an ECD or NPD, however, are only achieved if the mass spectrometer is operated under selected ion monitoring (SIM). Nitrophenols are derivatized after extraction by heptafluorobutyric anhydride or by acetic anhydride where the latter method can be directly applied to the aqueous sample. The nitramine explosives, such as RDX, HMX, and tetryl, hexyl, the nitrate esters, such as nitropenta (PETN) and nitroguanidine as well as picric acid cannot, or only with difficulty, be analyzed by gas chromatography. They may be determined by high performance liquid chromatography (HPLC) with UV-detection. The HPLC analysis can be extended to include also nitrotoluenes and nitroaminotoluenes.