Analysis of Nitroaromatics and Nitramines in Ammunition Waste Water and in Aqueous Samples from Former Ammunition Plants and Other Military Sites Analyse von Nitroaromaten und Nitraminen in Munitionsabwasser und wäßrigen Proben ehemaliger Munitionsfabriken und anderen Rüstungsaltlasten

Abstract

Summary: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 byproducts 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 2 85%) provided they contain only one amino group. Nitrotoluenes, chlorinated nitrobenzenes and aminonitrotoluenes (nitrotoluidines) may be determined by gas chromatography (GC) using selctive 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 (GUMS) 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.

Simultaneous Biodegradation of 2,4-Dinitrotoluene and 2,6-Dinitrotoluene in an Aerobic Fluidized-Bed Biofilm Reactor

“…The production of TNT required large amounts of water for the purification of the product. Therefore, ammunition plants were often located near large groundwater reservoirs (3). Improper disposal practices associated with TNT manufacturing have resulted in contamination of soils and waters with dinitrotoluenes.…”

Analysis of nitrogen‐based explosives with desorption atmospheric pressure photoionization mass spectrometry

“…In GC, picric acid has been reported to adsorb strongly on polar surfaces (e.g. the GC column), which causes serious peak tailing and prevents its analysis by this technique . Therefore, we suggest that also here picric acid is strongly adsorbed on the sampling surface and/or surfaces of the MS inlet, which leads to poor desorption efficiency.…”

Ion spectrometric detection technologies for ultra‐traces of explosives: A review

“…In its applications in the aquatic environment, nitroaromatic explosives and their degradation products in water samples can be detected by using LC-MS (Gates et al, 1996). The nitroaromatic and nitramines and their metabolites present in former military sites have been investigated using GC-MS (Levsen et al, 1993). EI-MS has been used to analyze the metabolites of PETN (Binks et al, 1996).…”