Uptake and fate of hexahydro-1,3,5-trinitro-1,3,5-triazine by Chrysopogon zizanioides

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a nitramine compound that has been used heavily by the military as an explosive. Manufacturing, use, and disposal of RDX have led to several contamination sites across the United States. RDX is both persistent in the environment and a threat to human health, making its remediation vital. The use of plants to extract RDX from the soil and metabolize it once it is in the plant tissue, is being considered as a possible solution. In the present study, the tropical grass Chrysopogon zizanioides was grown hydroponically in the presence RDX at 3 different concentration levels: 0.3, 1.1, and 2.26 ppm. The uptake of RDX was quantified by high performance liquid chromatography (HPLC) analysis of media samples taken every 6 hr during the first 24 hr and then daily over a 30-day experimental period. A rapid decrease in RDX concentration in the media of both controls and plant treatments was seen within the first 18 hours of the experiment with the greatest loss in RDX over time occurring within the first 6 hours of exposure. The loss was similar in both controls and plant exposures and possibly attributed to rapid uptake by the containers. A plant from one treatment at each of the three concentrations was harvested at Day 10, 20 and 30 throughout the experiment and extracted to determine the localization of RDX within the tissue and potentially identify any metabolites on the basis of differing retention times. Of the treatments containing 0.3, 1.1, and 2.26 ppm RDX, 13.1%, 18.3%, and 24.2% respectively, was quantified in vetiver extracts, with the majority of the RDX being localized to the roots. All plants not yet harvested were harvested on Day 30 of the experiment. A total of three plants exposed to each concentration level as well as the control, were extracted and analyzed with HPLC to determine amount of RDX taken up, localization of RDX within the plant tissue, and potentially identify any metabolites. Phytotoxicity of RDX to vetiver was also monitored. While a loss in biomass was observed in plants exposed to all the different concentrations of RDX, control plants grown in media not exposed to RDX showed the greatest biomass loss of all the treatments. There was also little variation in chlorophyll content between the different concentration treatments with RDX. This preliminary greenhouse study of RDX uptake 10 by Chrysopogon zizanioides will help indicate the potential ability of vetiver to serve as a plant system in the phytoremediation of RDX.

Intergranular Corrosion and Stress Corrosion Cracking of Extruded AA6005A

A research program focused on understanding the intergranular corrosion (IGC) and stress corrosion cracking (SCC) behavior of AA6005A aluminum extrusions is presented in this dissertation. The relationship between IGC and SCC susceptibility and the mechanisms of SCC in AA6005A extrusions were studied by examining two primary hypotheses. IGC susceptibility of the elongated grain structure in AA6005A exposed to low pH saltwater was found to depend primarily on the morphology of Cu-containing precipitates adjacent to the grain boundaries in the elongated grain structure. IGC susceptibility was observed when a continuous (or semi-continuous) film of Cu-containing phase was present along the grain boundaries. When this film coarsened to form discrete Cu-rich precipitates, no IGC was observed. The morphology of the Cu-rich phase depended on post-extrusion heat treatment. The rate of IGC penetration in the elongated grain structure of AA6005A-T4 and AA6005A-T6 extrusions was found to be anisotropic with IGC propagating most rapidly along the extrusion direction, and least rapidly along the through thickness direction. A simple 3-dimensional geometric model of the elongated grain structure was accurately described the observed IGC anisotropy, therefore it was concluded that the anisotropic IGC susceptibility in the elongated grain structure was primarily due to geometric elongation of the grains. The velocity of IGC penetration along all directions in AA6005A-T6 decreased with exposure time. Characterization of the local environment within simulated corrosion paths revealed that a pH gradient existed between the tip of the IGC path and the external environment. Knowledge of the local environment within an IGC path allowed development of a simple model based on Fick's first law that considered diffusion of Al3+ away from the tip of the IGC path. The predicted IGC velocity agreed well with the observed IGC velocity, therefore it was determined that diffusion of Al3+ was the primary factor in determining the velocity of IGC penetration. The velocity of crack growth in compact tensile (CT) specimens of AA6005A-T6 extrusion exposed to 3.5% NaCl at pH = 1.5 was nearly constant over a range of applied stress intensities, exposure times, and crack lengths. The crack growth behavior of CT specimens of AA6005A-T6 extrusion exposed to a solution of 3.5% NaCl at pH = 2.0 exhibited similar behavior, but the crack velocity was ~10.5X smaller than that those exposed to a solution at pH =1.5. Analysis of the local stress state and polarization behavior at the crack tip predicted that increasing the pH of the bulk solution from 1.5 to 2.0 would decrease the corrosion current density at the crack tip by approximately 11.8X. This predicted decrease in corrosion current density was in reasonable agreement with the observed decrease in SCC velocity associated with increasing the solution pH from 1.5 to 2.0. The agreement between the predicted and observed SCC velocities suggested that the electrochemical reactions controlling SCC in AA6005A-T6 extrusions are ultimately controlled by the pH gradient that exists between the crack tip and external environment.