Abstract
Although much has been discovered, discussed and written as to problems ofcontamination by various military unique compounds, particularly by the nitrogen basedenergetics (NOCs), remaining problems dictate further evaluation of actual and potentialrisk to the environment by these energetics and their derivatives and metabolites throughdetermination of their environmental impact—transport, fate and toxicity. This workcomprises an effort to understand structural relationships and degradation mechanisms ofcurrent and emerging explosives, including nitroaromatic; cyclic and cage cyclic nitramine;and a nitrocubane. This review of our computational chemistry and spectroscopic researchdescribes and compares competitive degradation mechanisms by free radical oxidative,reductive and alkali hydrolysis, relating them, when possible, to environmental risk.
Highlights
It is well known that actual and potential environmental risk assessment of nitrogen based energetic compounds (NOCs) is greatly complicated by the potential of these reactive compounds to form large numbers of environmental transformation products that can exhibit a wide range of physical properties and reactivities
TNT was chemically transformed into products with high biodegradability by utilizing nucleophilic reactions with sodium hydroxide (NaOH) or with calcium hydroxide (Ca[OH]2) as hydrolyzing agents, thereby initiating complex competing reactions in which time and nucleophilic concentration influenced production of mono- and di-hydroxylated aromatic intermediates
2,6- and 2,4-dinitrotoluenes were included in the comparison as to formation, steric, highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energies, and dipole moments
Summary
It is well known that actual and potential environmental risk assessment of nitrogen based energetic compounds (NOCs) is greatly complicated by the potential of these reactive compounds to form large numbers of environmental transformation products that can exhibit a wide range of physical properties and reactivities. As computational and experimental data is compiled, the continuous accumulation of information can be expected to provide environmental scientists with means to expedite assessment of environmental risk as well as to prioritize emerging compounds for research and management [54,55,56,57,58,59,60,61] This discussion of competitive degradation mechanisms of NOCs by free radical oxidative, reductive and alkaline hydrolysis deals with i) nitroaromatics: 2,4,6-trinitrotoluene (TNT); 1,3,5trinitrobenzene (TNB); 2,4,6-trinitrophenol (TNP or picric acid); ii) cyclic nitramines: hexahydro1,3,5-trinitro-1,3,5-triazine (RDX); octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX); iii) cage cyclic nitramines: 2,4,6,8,10,12-hexanitrohexa-azoisowurtzitane (CL-20); and 2,4,6,8tetranitro1,3,5,7-tetraaza-cubane (TNTAC), predicted but not yet synthesized; and iv) cage cubane: octonitrocubane (ONC). Where spectroscopic verification is used, it is described in the sections discussing the various compounds
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