Environmental process descriptors for TNT, TNT-related compounds and picric acid in marine sediment slurries.

Process descriptors were determined for picric acid, TNT, and the TNT-related compounds 2,4DNT, 2,6DNT, 2ADNT, 4ADNT, 2,4DANT, 2,6DANT, TNB and DNB in marine sediment slurries. Three marine sediments of various physical characteristics (particle size ranging from 15 to >90% fines and total organic carbon ranging from <0.10 to 3.60%) were kept in suspension with 20ppt saline water. Concentrations of TNT and its related compounds decreased immediately upon contact with the marine sediment slurries, with aqueous concentrations slowly declining throughout the remaining test period. Sediment-water partition coefficients could not be determined for these compounds since solution phase concentrations were unstable. Kinetic rates and half-lives were influenced by the sediment properties, with the finer grained, higher organic carbon sediment being the most reactive. Aqueous concentrations of picric acid were very stable, demonstrating little partitioning to the sediments. Degradation to picramic acid was minimal, exhibiting concentrations at or just above the detection limit.

Comparison of environmental fate and transport process descriptors of explosives in saline and freshwater systems.

Environmental process descriptors are necessary to evaluate the fate and transport of munitions constituents that have been introduced into the environment. An extensive database exists for freshwater environments; however, explosives fate and transport parameters such as dissolution rates, transformation rates, and adsorption of explosives have not been evaluated under both freshwater and saline conditions to determine the applicability of the freshwater data to saline environments. The objective of this study was to determine if freshwater fate and transport processes were similar to those determined under saline water conditions. We evaluated TNT, RDX, and HMX dissolution rates, transformation rates, and adsorption under freshwater and saline conditions in batch tests. Results showed a generally close agreement. Therefore, the existing freshwater database for explosives fate and transport process descriptors can be used in marine environments.

Vapor-phase transport of explosives from buried sources in soils.

The fate and transport of explosives in the soil pore vapor spaces affects both the potential detection of buried ordnance by chemical sensors and vadose zone transport of explosives residues. The efficacy of chemical sensors and their potential usefulness for detecting buried unexploded ordnance (UXO) is difficult to determine without understanding how its chemical signatures are transported through soil. The objectives of this study were to quantify chemical signature transport through soils under various environmental conditions in unsaturated soils and to develop a model for the same. Flux chambers, large soil containers, and batch tests were used to determine explosives signature movement and process descriptors for model development. Low signatures were observed for explosives (2,4-dinitrotoluene, 2,6-dinitrotoluene, and 1,3-dinitrobenzene) under all environmental conditions. A diffusion model was used to describe the chemical transport mechanism in the soil pore air. The soil-air partition constant was treated as a fit parameter in the model owing to the uncertainty in its a priori estimation. The model predictions of the trends in experimental fluxes and the soil concentration were only marginal at best. It was concluded that better estimates of the partition constant are required for more accurate estimation of the chemical concentration at the soil-air interface. Chemical sensors will need to be very sensitive because of low signatures. However, this may result in many false alarms because of explosives residues not associated with UXO on firing ranges. Low explosives signatures also should result in insignificant air environmental exposures.

An exploratory approach to modeling explosive compound persistence and flux using dissolution kinetics.

Recent advances in the description of aqueous dissolution rates for explosive compounds enhance the ability to describe these compounds as a contaminant source term and to model the behavior of these compounds in a field environment. The objective of this study is to make predictions concerning the persistence of 2,4,6-trinitrotoluene (TNT) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in solid form both as individual explosive compounds and components of octol, and the resultant concentrations of explosives in water as a result of dissolution using three exploratory modeling approaches. The selection of dissolution model and rate greatly affect not only the predicted persistence of explosive compound sources but also their resulting concentrations in solution. This study identifies the wide range in possible predictions using existing information and these modeling approaches to highlight the need for further research to ensure that risk assessment, remediation and predicted fate and transport are appropriately presented and interpreted.

Volatilization of contaminants from suspended sediment in a water column during dredging.

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.

Vapor phase transport of unexploded ordnance compounds through soils.

Unexploded ordnance (UXO) is a source of concern at several U.S. Department of Defense (DOD) sites. Localization of munitions and fate and transport of the explosive compounds from these munitions are a major issue of concern. A set of laboratory experiments were conducted in specially designed flux chambers to measure the evaporative flux of three explosive compounds (2,4-dinitrotoluene, 2,6-dinitrotoluene, and 1,3-dinitrobenzene) from three different soils. The effect of different soil moisture contents, the relative humidity of air contacting the soil surface, and soil temperature on the chemical fluxes were evaluated. A diffusion model was used to describe the chemical transport mechanism in the soil pore air. The soil-air partition constant was treated as a fit parameter in the model because of the uncertainty in the a priori estimation. The model predicts the qualitative trends of the experimental fluxes satisfactorily. Under extremely dry conditions, the flux decreased more rapidly than that predicted by the model. The fluxes from soils at 24 degrees C were higher than those at 14 degrees C, indicating a larger volatilization driving force at the higher temperature.

Dissolution rates of three high explosive compounds: TNT, RDX, and HMX.

Incidental exposure to high explosive compounds can cause subtle health effects to which a population could be more susceptible than injury by detonation. Proper source characterization is a key requirement in the conduct of risk assessments. For nonvolatile solid explosives, dissolution is one of the primary mechanisms that controls fate and transport, resulting in exposure to these compounds remote from their source. To date, information describing dissolution rates of high explosives has been sparse. The objective of this study was to determine the dissolution rates of three high explosive compounds, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), in dilute aqueous solutions as a function of temperature, surface area, and energy input. To determine each variable's impact on dissolution rate, experiments were performed where one variable was changed while the other two were held constant. TNT demonstrated the fastest dissolution rate followed by HMX and then RDX. Dissolution rate correlation equations were developed for each explosive compound incorporating the three aforementioned variables, independently, and collectively in one correlation equation.