Nitroaromatic compounds, including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3, 5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5-tetrazocine (HMX), N-methyl-N,2,4,6-tetranitroaniline (tetryl), and associated byproducts and degradation products, were released to the environment during manufacturing and load, assembly, and pack (LAP) processes at U.S. Army Ammunition Plants (AAPs) and other military facilities. As a result of the release of these nitroaromatic compounds into the environment, many AAPs have been placed on the National Priorities List for Superfund cleanup (Fed. Reg. 60:20330). Many of these sites cover a wide expanse of relatively undisturbed land and provide diverse habitats that support a variety of aquatic and terrestrial species. Nitroaromatics are potentially toxic to the indigenous species at these sites and present a significant concern for site remediation. Table 1 presents an overview of ranges of detected concentrations of the nitroaromatic compounds in groundwater, surface water, sediment, and soil at military and manufacturing sites.

Nitroaromatic Munition Compounds: Environmental Effects and Screening Values

Determination of polycyclic aromatic compounds emitted from brown-coal-fired residential stoves by gas chromatography/mass spectrometry

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 ≥85%) provided they contain only one amino group. Nitrotoluenes, chlorinated nitrobenzenes and aminonitrotoluenes (nitrotoluidines) may be determined by gas chromatography (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.



Abwasser von Anlagen zur Herstellung von Explosivstoffen sowie Wasserproben (Grund- und Oberflachenwasser) auf oder nahe fruherer Anlagen zur Produktion oder Abfullung von Sprengstoffen konnen durch die ursprunglichen Explosivstoffe, insbesondere Nitrotoluole (wie Dinitrotoluole, 2,4,6-Trinitrotoluol (TNT)) sowie Nitramine (wie Hexogen (RDX), Octogen (HMX) und Tetryl) sowie Hexyl, aber auch durch Nebenprodukte wie chlorierte Nitrobenzole und Nitrophenole, sowie Verbindungen, die durch biologischen Abbau entstanden sind, wie Aminonitrotoluole, kontaminiert sein. Die Verbindungen lassen sich aus wassrigen Proben durch flussig/flussig-Extraktion (unter Verwendung von Dichlormethan oder Toluol) oder durch Festphasenextraktion (unter Verwendung modifizierten Silicagels) mit hohen Wiederfindungen (in der Regel ≥85%) extrahieren, solange diese Verbindungen nur eine Aminofunktion besitzen. Nitrotoluole, chlorierte Nitrobenzole und Aminonitrotoluole lassen sich mit Hilfe der Gaschromatographie unter Verwendung eines Elektroneneinfangdetektors (ECD), eines Stickstoff-Phosphor-Detektors (NPD) oder eines Chemilumineszenzdetektors („thermal energy analyzer, TEA”) bestimmen. Der Einsatz der gekoppelten Gaschromatographie/Massenspektrometrie (GC/MS) unter Elektronenstosbedingungen ist noch spezifischer. Nachweisgrenzen, die mit dem eines NPD-Detektors vergleichbar sind, werden jedoch nur erreicht, wenn das Massenspektrometer unter den Bedingungen des „selected ion monitoring (SIM)” arbeitet. Nitrophenole werden nach der Extraktion mit Heptafluorbuttersaureanhydrid bzw. Essigsaureanhydrid derivatisiert (wobei die zweite Methode direkt auf die wasrige Probe angewandt werden kann). Die Nitraminsprengstoffe RDX, HMX und Tetryl, aber auch Hexyl, Nitratester wie Nitropenta (PETN) sowie schlieslich Nitroguanidin und Pikrinsaure lassen sich nicht oder nur mit Schwierigkeiten mit Hilfe der Gaschromatographie analysieren. Sie konnen mit Hilfe der Hochleistungsflussigchromatographie (HPLC) mit UV-Detektion bestimmt werden. Die HPLC-Analyse kann so modifiziert werden, das sie auch Nitrotoluole und Nitroaminotoluole erfast.

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

Ambient mass spectrometry has evolved rapidly over the past decade, yielding a plethora of platforms and demonstrating scientific advancements across a range of fields from biological imaging to rapid quality control. These techniques have enabled real-time detection of target analytes in an open environment with no sample preparation and can be coupled to any mass analyzer with an atmospheric pressure interface; capabilities of clear interest to the defense, customs and border control, transportation security, and forensic science communities. This review aims to showcase and critically discuss advances in ambient mass spectrometry for the trace detection of explosives.

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W.T. Bolleter

Papers

Liquid chromatographic determination of nitroglycerin products in waste waters

Gas chromatographic analysis of trinitrotoluene from the continuous process

Quantitative Liquid Chromatographic Analysis of Propellants Containing Nitroglycerin

Application of thin-layer chromatography for improving the continuous TNT process

Continuous TNT process studies