Stability of immobilized 2,4,6-trinitrotoluene metabolites in soil under long-term leaching conditions.

2,4,6-Trinitrotoluene (TNT)-contaminated soil was remediated by an anaerobic/aerobic slurry process. Prior to treatment, the soil was spiked with [14C]-TNT. Leaching experiments were carried out with the decontaminated soil to determine the degree of binding of the radiolabel under a variety of conditions. To simulate natural degradation processes of soil organic matter, each of three columns was subjected to a different treatment known to enhance biological transformation over a 92-week period. Only minor amounts of radioactivity (1.0% of the bound radioactivity) were released from treated soil incubated in the presence of the lignin-degrading fungus Phanerochaete chrysosporium. Simulation of seasonal variation in temperature, including freezing of the soil, did not cause a significant release of radioactivity (1.4%). Growth and flowering of the bush bean Phaseolus vulgaris only released 0.8% of the bound radioactivity to the eluate; however, during the decomposition phase, an additional 7.7% of the bound radioactivity was released. We propose that this radioactivity was bound to soluble humic material that was mobilized due to a pH shift during the decomposition of the plant organic matter. This is supported by the observation that neither free TNT nor its metabolites were present in the eluate. During the different incubation experiments, 3.9 to 8.5% of the bound radioactivity was found as 14CO2. The results indicate a slow turnover of even strongly bound immobilized metabolites of TNT.

Solid-state nitrogen-15 nuclear magnetic resonance analysis of biologically reduced 2,4,6-trinitrotoluene in a soil slurry remediation.

Soil contaminated with 2,4,6-trinitrotoluene (TNT) and spiked with [14C]- and [15N3]-TNT was subjected to an anaerobic-aerobic soil slurry treatment and subsequently analyzed by radiocounting and solid-state 15N nuclear magnetic resonance (NMR) spectroscopy. This treatment led to a complete disappearance of extractable radioactivity originating from TNT and almost all of the radioactivity was recovered in the insoluble soil fraction. As revealed by solid-state 15N NMR, a major fraction of partially reduced metabolites of TNT was immobilized into the soil during the early stage of the anaerobic treatment, although some of the compounds (i.e., aminodinitrotoluenes and azoxy compounds) were extractable by methanol. Considerable 15N intensity was assigned to condensation products of TNT metabolites. A smaller signal indicated the formation of azoxy N. This signal and the signal for nitro groups were not observed at the end of the anaerobic phase, revealing further reduction and/or transformation of their corresponding compounds. An increase of the relative proportion of the condensation products occurred with increasing anaerobic incubation. Aerobic incubation resulted in a further decrease of aromatic amines, presumably due to oxidative transformations or their involvement in further condensation reactions. The results of the study demonstrate that the anaerobic-aerobic soil slurry treatment represents an efficient strategy for immobilizing reduced TNT in soils.