In this research, a risk assessment was undertaken in order to develop the remediation and management strategy of a contaminated gunnery site, where a nearby flood controlling reservoir is under construction. Six chemicals, including explosives and heavy metals, posing potential risk to environmental and human health, were targeted in this study. A site-specific conceptual site model was constructed, based on effective, reasonable exposure pathways, to avoid any overestimation of the risk. Also, conservative default values were adapted to prevent underestimation of the risk when site-specific values were not available. The risks posed by the six contaminants were calculated using the API's Decision Support System for Exposure and Risk Assessment, with several assumptions. In the crater-formed-area (Ac), the non-carcinogenic risks (i.e., HI values) of tri-nitro-toluene (TNT) and Cd were slightly larger than 1, but for RDX (Royal Demolition Explosives) was over 50. The total non-carcinogenic risk of the whole gunnery range was calculated to be 62.5, which was a significantly high value. The carcinogenicity of Cd was estimated to be about 10(-3), while that for Pb was about 5 x 10(-4), which greatly exceeded the generally acceptable carcinogenic risk level of 10(-4)-10(-6). It was concluded from the risk assessment that there is an immediate need for remediation of both carcinogens and non-carcinogens before construction of the reservoir. However, for a more accurate risk assessment, further specific estimations of the changes in environmental conditions due to the construction of the reservoir will be required; and more over, the effects of the pollutants to the ecosystem will also need to be evaluated.
Phenanthrene and pyrene were not transformed by birnessite (␦-MnO 2 ) in the presence of phenol. The phenoxy radicals generated from phenol by birnessite did not act as a mediator for polycyclic aromatic hydrocarbon radical reaction under the studied conditions. In contrast, 9-hydroxyphenanthrene and 1-hydroxypyrene were remarkably sensitive to birnessite. The disappearance patterns of the test compounds both in the aqueous phase and soil followed first-order kinetics, with a linear relationship found between the rate constants and the surface area of birnessite. Moreover, the data indicated that the reaction was faster in the presence of soil than in the aqueous phase probably because of the presence of hydroxyl groups in soil organic matter. Sequential solvent extraction was not successful in the recovery of 9-hydroxyphenanthrene from the birnessite-treated soil samples, and capillary electrophoresis data suggest the formation of nonextractable residues of the compound in soil. In addition, the acute toxicity determined by Microtox declined approximately 8.3 times in the soil samples treated with birnessite compared to untreated samples, demonstrating that the toxic compound was no longer present as its parent form.
Oxidative coupling reaction of phenol mediated by birnessite was studied in aqueous phase and soil. Phenol was readily transformed by birnessite and almost all phenol disappeared in both samples after 24 hours of reaction. Phenol transformation kinetics was investigated by plotting reaction time against logarithm concentrations of residual phenol, revealing that exponential decrease of phenol was evident both in aqueous phase and soil, and maximum removal rates were 2.31-2.54 times higher in the presence of soil. Reaction products of phenol were identified by LC-MS and capillary electrophoresis. In aqueous phase, polyphenols were formed by self-coupling reaction of phenoxy radicals whereas phenol was found to be present as bound residues in soil, probably due to the cross-coupling reaction between the radicals and soil organic matter. Microtox System was employed to determine the toxicity after birnessite treatment, and the toxicity of phenol-spiked solution and soil samples decreased remarkably compared to that of phenol solution before treatment.
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