Movement of TNT and RDX from composition B detonation residues in solution and sediment during runoff.

Energetics used in military exercises can potentially contaminate ground and surface waters. This study was conducted to evaluate the movement of Composition B, a formulation that includes 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), in runoff. Mechanisms of transport we examined include movement of energetics dissolved in runoff, as particles and adsorbed to suspended sediment, and in infiltration. Rainfall simulations were conducted under controlled conditions with two rainfall rates (approximately 30 and 50 mm h-1), two soils with different infiltration capacities, and four energetic particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). Particles remaining on the soil surface after rainfall were measured as well as energetics dissolved in runoff, in suspended sediment, and in infiltration. Greater concentrations of TNT than RDX and HMX were found dissolved in runoff due to its higher solubility and dissolution rates. We also found that particle transport in runoff increased with decrease in particle size. Smaller particle sizes also led to greater transport dissolved in solution. Relationships were found relating runoff and sediment yield to the transport of RDX and TNT. The results of this study allow improved prediction of Composition B transport in runoff and therefore its contamination potential.

The thermal decomposition process of Composition B by ReaxFF/lg force field.

Composition B is a melt-cast explosive consisting of mixtures of TNT and RDX. It has many excellent properties, but there are still multiple safety problems when it is used. Therefore, it is of importance to understand the thermal decomposition mechanism of Composition B. In this paper, during the establishment of the supercell model, the mass ratio of TNT to RDX is about 2:3, which accords with the actual proportion of formula of Composition B. Afterward, the thermal decomposition reaction of Composition B is conducted at various temperatures (2000 K, 2500 K, 3000 K, 3500 K, and 4000 K) by using molecular dynamics simulation of ReaxFF/lg. In terms of potential energy (PE) evolution, primary reaction, intermediate product, final product, and clusters, the thermal decomposition mechanism of Composition B is made an analysis. The activation energy of Composition B is 141.8 kJ/mol by fitting the kinetic parameters of the reaction. During the decomposition process of Composition B, the decay rate of RDX is faster than that of TNT, and the decay rates of TNT and RDX is accelerated significantly with the increasing temperature. The higher the temperature, the shorter the time difference between the two to fully decompose. It can be revealed from the result that the initial reaction path of Composition B decomposition is N-NO2 of RDX cleavage to form NO2, followed by the reaction of TNT with NO2 and other molecules. The initial decomposition reaction path of Composition B is the similar at different temperatures. The main products are small molecules (NO2, NO, N2O, H2O, CO2, N2, H2, HNO2, and HNO). Temperature can make a great difference for the structure of clusters. Large clusters in the system will break down into smaller molecules at high temperature.

Multiple metrics quantify and differentiate responses of vegetation to composition B.

Quantifying vegetation response to explosive compounds has focused predominantly on morphological impacts and uptake efficiency. A more comprehensive understanding of the total impacts of explosives on vegetation can be gained using a multivariate approach. We hypothesized that multiple variables representing morphological and physiological responses will more clearly differentiate species and treatments than any single variable. Individuals of three plant species were placed in soils contaminated with Composition B, which comprises 60% hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 40% 2,4,6-trinitrotoluene (TNT), and grown for 2 months. Response metrics used included photosynthetic operation, water relations, growth characteristics, as well as nitrogen and carbon concentrations and isotopic compositions. Individual metrics showed high variability in response across the three species tested. Water relations and nitrogen isotopic composition exhibited the most consistent response across species. By comparing multiple variables simultaneously, better separation of both species and exposure was observed. The inclusion of novel metrics can reinforce previously established concepts and provide a new perspective. Additionally, the inclusion of various other metrics can greatly increase the ability to identify and differentiate particular groups. By using multivariate analyses and standard vegetation metrics, new aspects of the vegetation response to explosive compounds can be identified.

Numerical analysis of thermal decomposition for RDX, TNT, and Composition B.

Demilitarization of waste explosives on a commercial scale has become an important issue in many countries, and this has created a need for research in this area. TNT, RDX and Composition B have been used as military explosives, and they are very sensitive to thermal shock. For the safe waste treatment of these high-energy and highly sensitive explosives, the most plausible candidate suggested has been thermal decomposition in a rotary kiln. This research examines the safe treatment of waste TNT, RDX and Composition B in a rotary kiln type incinerator with regard to suitable operating conditions. Thermal decomposition in this study includes melting, 3 condensed phase reactions in the liquid phase and 263 gas phase reactions. Rigorous mathematical modeling and dynamic simulation for thermal decomposition were carried out for analysis of dynamic behavior in the reactor. The results showed time transient changes of the temperature, components and mass of the explosives and comparisons were made for the 3 explosives. It was concluded that waste explosives subject to heat supplied by hot air at 523.15K were incinerated safely without any thermal detonation.

Production of particulate Composition B during simulated weathering of larger detonation residues.

Explosives and energetics continue to be prominent contaminants on many military installations. This research was undertaken to understand the extent to which microscale (10's of µm) particles are produced when macroscale residues are weathered by artificial precipitation. Initial experiments, in which artificial rainwater was applied drip-wise to single chunks of Composition B detonation residues from multiple heights, confirmed that microscale particles were produced during precipitation-driven aging, with 30% of the explosive mass collected detected as particulate Composition B (e.g., particles >0.45 µm in diameter). Follow-on experiments, during which multiple cm-sized residue chunks were subjected to realistic simulated precipitation, demonstrated an initial large pulse of particulate Composition B, followed by sustained production of microscale particles that represented 15-20% of recovered explosives. These findings indicate that the effective footprint of detonation residues likely increases as particulates are produced by the production and spreading of microscale particles across the soil surface. Combined with results published elsewhere that microscale particles can move into porous media to become a distributed source term, these findings point to the need for inclusion of these processes in explosive contaminant fate and transport modeling.

Transport and dissolution of microscale Composition B detonation residues in porous media.

The deposition of military explosive residues on training ranges has resulted in extensive contamination of land and water resources. Experiments were performed to examine the transport and dissolution of mm-sized and microscale Composition B (Comp B) residues applied to the top of sand columns under unsaturated flow conditions. Under a continuous application of artificial rainwater, greater dissolved effluent concentrations of TNT and RDX (5- and 10-fold, respectively) were observed for the columns amended with microscale residues than for the columns amended with the mm-sized residues. This difference between microscale and mm-sized residues likely was due, in part, to dissolution of microscale particles entrapped in the sand column. Elution of particulate Comp B from the columns, based on the difference between total and dissolved explosives concentrations in column effluent, indicated higher and more frequent detections of particulate explosives in the columns amended with microscale Comp B than the columns amended with mm-sized Comp B. Examination of the vertical profiles of explosives in sand indicated that particulate residues had migrated into the sand, with a greater particulate mass observed in the columns which had received the microscale Comp B compared to those which received the mm-sized Comp B. These results indicate that both mm-sized and microscale detonation residues can contribute to the undissolved (e.g., particulate) Comp B transport into to the subsurface. This particulate transport increases the effective contact time between residues and infiltrating rainwater, leading to overall increases in the dissolved mass contaminant flux.