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The purpose of this thesis is to evaluate the performance and cost effectiveness of a Peroxone Groundwater Treatment Plant (PGTP) designed and operated by Montgomery Watson, in support of the Defense Evaluation Support Agency's independent analysis for the United States Army Environmental Center (USAEC). Many Department of Defense installations have sites that contain groundwater contaminated with explosive materials. Primary methods for the removal of explosive materials involve the use of Granular Activated Carbon (GAC). This process, however, requires additional waste disposal and treatment of explosive laden GAC, thereby incurring additional costs. An alternate method for the treatment of contaminated groundwater involves the use of hydrogen peroxide (H2O2) in conjunction with ozone (03). This method is referred to as the Peroxone oxidation process. A demonstration of the PGTP was conducted from 19 August to 8 November, 1996, at Cornhusker Army Ammunition Plant (CAAP), Grand Island, Nebraska using a small scale version with a maximum flow rate of 25 gallons per minute. The explosive contaminants analyzed during the demonstration include 2,4,6-Trinitrotoluene (TNT), 1,3,5-Trinitrobenzene (TNB), 1,3,5-Triazine (RDX), and Total Nitrobodies. Peroxone cost effectiveness was evaluated using a 30 year life cycle cost comparison to GAC and Ultraviolet/Ozone processes

This thesis explores the development of direct electrochemical reduction as a means of providing primary treatment of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a manufacturing process waste stream. An industrial process wastewater laden with RDX was successfully treated in small batch reactors. Reaction kinetics were used to design a proof of concept bench scale flow reactor that utilized parallel packed electrode plates. Following successful testing of this reactor, a pilot scale packed electrode flow reactor was built. The reactor performance as a function of residence time was fit by a first order decay equation. Greater than 97% reduction of RDX in a process wastewater was observed at a reactor residence time of 27 minutes. The work presented herein was successful in creating an electrochemical treatment system capable of removing RDX from an industrial process waste stream with no chemical addition, and without creating an additional hazardous waste stream.

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In order to effectively model the behaviour of energetic materials under operational conditions it is essential to obtain detailed structural information for these compounds at elevated temperature and/or pressures. The structural characterisation of the high explosives RDX and CL-20 and a series of inorganic azides [Mn+(N3)n] at extreme conditions is described herein. In addition to the characterisation of a highly metastable β -form of RDX (1,3,5- trinitrohexahydro-1,3,5-triazine) at atmospheric pressure, the structure solution of a high-pressure/ high-temperature polymorph is described. This form, obtained above 4.3 GPa and 450 K, has been shown to be distinct from the β -form and has therefore been denoted - RDX. Furthermore, ε -RDX is sufficiently metastable to allow its recovery to ambient pressure at 150 K; it only transforms to the α -form upon warming to 230 K. Finally, the ambient-temperature compression of RDX has been investigated to a maximum pressure of 23.0 GPa, using methanol:ethanol (4:1) as the pressure-transmitting medium; no phase transition was observed under these conditions, other than the α → γ transition at 3.9 GPa. The structure of a high-pressure polymorph of CL-20 (2,4,6,8,10,12- hexanitrohexaazaisowurtzitane) has also been determined by a combination of powder and single-crystal X-ray diffraction. Compression of γ -CL-20 to above 0.7 GPa using Fluorinert (FC-77) as the pressure-transmitting medium results in a phase transition to the ζ -form, which has been found to display structural similarities with both theγ γ - and ε -forms. The high-pressure behaviour of CL-20, however, depends markedly on the starting polymorph and the pressure-transmitting medium selected. Compression of γ -CL-20 in MeOH:EtOH (4:1) results in the formation of a 2:1 CL-20:MeOH solvate at 0.5 GPa. This solvate is stable upon compression to P > 5.0 GPa. It may also be recovered to ambient pressure at 293 K. Meanwhile, no phase transition is observed during the compression of ε -CL-20 to a maximum pressure of 7.2 GPa. Finally, a series of inorganic azides [NaN3, CsN3, TlN3, NH4N3, AgN3 and Pb(N3)2] has been characterised under a range of pressure and temperature conditions. Of the six compounds studied, all displayed at least one polymorphic transition – 5 new forms have been structurally characterised in this work and evidence of another 5 is presented. The combined effect of pressure and temperature results in sodium azide adopting a tetragonal structure common to larger alkali metal azides. Caesium azide has been shown to undergo three phase transitions during compression to 6.0 GPa – the structure of the first high-pressure form is reported. A variable temperature X-ray powder diffraction study of TlN3 has allowed the structural characterisation of the low-temperature TlN3-IV (at 230 K) as well as providing evidence for a phase transition to a high-temperature form above 550 K. The high-pressure form III (obtained above 0.76 GPa) has also been determined by neutron powder diffraction. Silver, ammonium and lead(II) azides have all been shown to undergo a phase transition at high pressures. Compression of silver azide (P > 0.80 GPa) removes an orthorhombic distortion observed at atmospheric pressure, resulting in the tetragonal structure adopted by CsN3 and TlN3 under ambient conditions. Moreover, NH4N3 and Pb(N3)2 have been found to undergo phase transitions at 2.6 GPa, although their high-pressure structures have still to be determined.

Understanding the impacts of explosive contamination on vegetation is key to understanding explosives behavior in the environment. I quantified shrub growth responses to 1,3,5-trinitroperhydro-1,35-triazine (RDX) soil contamination across three life stages and I hypothesized that RDX would have the greatest impact on seed germination. Morella cerifera seeds were germinated on soils amended with RDX up to 1500 mg RDX kg-1 dry soil. Juvenile and adult individuals were exposed for 6 weeks to soil amended with RDX up to 750 and 1500 mg RDX kg-1 dry soil, respectively. Morphological responses were quantified for juveniles while physiological measurements were quantified for adults. RDX induced a significant response in all age groups and, in accordance with the hypothesis, germination was the most impacted of the three stages. Impacts varied by concentration in addition to life stage, showing that many variables influence plant response to RDX.

Poplar (Populus deltoides x nigra DN34) tissue cultures removed 2,4,6-trinitrotoluene (TNT) from an aqueous solution in five days, reducing the toxicity of the solution from highly toxic Microtox® EC value to that of the control. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) was taken up by the plant tissue cultures more slowly, but toxicity reduction of the solution was evident. The measurement of toxicity reduction of aqueous solutions containing TNT and RDX was performed using a novel methodology developed for use with the Microtox® testing system. Radiolabeled TNT and RDX were used to confirm removal of explosives from hydroponic solutions containing plant tissue cultures and to verify that toxicity did not change in solutions where no plant cultures were present (positive controls). High Performance Liquid Chromatography (HPLC) and Liquid Scintillation Counter (LSC) measurements confirmed removal of TNT and RDX from solutions containing poplar plant tissue cultures and constancy of the plant-free controls. In addition, metabolites were identified in remediated solutions by HPLC, confirming the mechanism by which plants can remediate groundwater, surface water, and soil solutions. Using an Affymetrix® microarray, poplar trees were exposed to TNT over 48 hours. General patterns, as well as significant downregulated and upregulated genes were studied. We identified several new genes that were implicated in the detoxification and metabolism of TNT by Populus. In particular, our results support the "green liver" model of different gene families being expressed during the time course experiments. This suggests an alignment with Phase I transformation, Phase II conjugation, and Phase III compartmentation processes. Many of the genes identified in this study were related to those significantly expressed in previous Arabidopsis studies, supporting the comparison between these two plants. Gene families represented as significant in this study were glucosyltransferases, glycosyltransferases, cytochromes, and phosphofructokinases. We saw patterns in the areas of respiration, citric acid cycle, shikimatic pathway, and toxic responses.

The energetic compounds TNT (2,4,6-trinitrotoluene), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) contaminate military testing ranges worldwide yet are known to be degraded by plants and microbes in the laboratory. However, these contaminants remain persistent in the environment and represent a health threat to both humans and ecosystems. The use of traditional soil remediation technologies, such as landfilling or incineration, require large excavation costs and disrupt the ecology of the site. Phytoremediation, the use of green plants for the in situ treatment of contaminants, may be the most appropriate means of treating energetic residues present at military testing ranges. Eglin Air Force Base (EAFB), located near Niceville, FL, is one of the largest military installations in the world and holds many plant and animal species which are threatened or endangered. The use of explosives during training exercises on firing ranges at EAFB has resulted in contamination of energetics on range soils. In an effort to increase range sustainability with respect to explosives contamination, EAFB has been established as the site where phytoremediation processes will be explored for this research.

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