Michael R. Walsh

Field Observations of the Persistence of Comp B Explosives Residues in a Salt Marsh Impact Area

Field observations of weathering Comp B (RDX/TNT 60/40) residue were made on a live-fire training range over four years. The Comp B residue was formed by low-order detonations of 120-mm mortar projectiles. Physical changes were the disaggregation of initially solid chunks into masses of smaller diameter pieces and formation of red phototransformation products that washed off with rain or tidal flooding. Disaggregation increased the surface area of the residue, thereby increasing the potential for dissolution. The bulk of the mass of Comp B was in the craters, but solid chunks were scattered asymmetrically up to 30m away.

Outdoor dissolution of detonation residues of three insensitive munitions (IM) formulations

We seek to understand the environmental fate of three new insensitive munitions, explosive formulations developed to reduce the incidence of unintended detonations. To this end, we measured the size distribution of residues from low order detonations of IMX 101, IMX 104, and PAX 21-filled munitions and are studying how these three formulations weather and dissolve outdoors. The largest pieces collected from the detonations were centimeter-sized and we studied 12 of these in the outdoors test. We found that the particles break easily and that the dissolution of 2,4-dinitroanisole (DNAN) is quasi-linear as a function of water volume. DNAN is the matrix and the least soluble major constituent of the three formulations. We used DNANs linear dissolution rate to estimate the life span of the pieces. Particles ranging in mass from 0.3 to 3.5 g will completely dissolve in 3-21 years given 100 cm y(-1) precipitation rates.

Energetic residues from field disposal of gun propellants

Military training with howitzers and mortars produces excess propellant that is burned on the training range and can result in point sources containing high concentrations of unreacted propellant constituents. Propellants contain energetic compounds such as nitroglycerin (NG) and 2,4-dinitrotoluene (2,4-DNT), both of which are found at firing positions and propellant disposal areas. To quantify the mass of residue remaining from the field-expedient disposal of propellants, two mortar propellants and one howitzer propellant were burned under different field conditions. These conditions included burning on a snow pack, at the bottom of a snow pit, and in a pan surrounded by snow for the mortar propellants and on dry and wet sand for the howitzer propellant. For the mortar propellant, the energetics (NG) remaining after burning in the bowl, on frozen ground, and on snow were 0.21%, 5.2% and 18%, respectively. For the howitzer propellant, the difference in energetics (2,4-DNT) remaining after disposal on wet and dry sand was <0.1%, with the overall residue rate of around 1%, similar to that for the mortar propellant burned in an open container. These tests demonstrate that environmental factors, especially in winter, can play a significant role in the effectiveness of field-expedient disposal of propellants.

Insights into the dissolution and the three-dimensional structure of insensitive munitions formulations

Two compounds, 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) are the main ingredients in a suite of explosive formulations that are being, or soon will be, fielded at military training ranges. We aim to understand the dissolution characteristics of DNAN and NTO and three insensitive muntions (IM) formulations that contain them. This information is needed to accurately predict the environmental fate of IM constituents, some of which may be toxic to people and the environment. We used Raman spectroscopy to identify the different constituents in the IM formulations and micro computed tomography to image their three-dimensional structure. These are the first three-dimensional images of detonated explosive particles. For multi-component explosives the solubility of the individual constituents and the fraction of each constituent wetted by water controls the dissolution. We found that the order of magnitude differences in solubility amongst the constituents of these IM formulations quickly produced hole-riddled particles when these were exposed to water. Micro-computed tomography showed that particles resulting from field detonations were fractured, producing conduits by which water could access the interior of the particle. We think that micro-computed tomography can also be used to determine the initial composition of IM particles and to track how their compositions change as the particles dissolve. This information is critical to quantifying dissolution and developing physically based dissolution models.

Remediation methods for white phosphorus contamination in a coastal salt marsh

With the closure of many military bases worldwide and a closer scrutiny of practices on remaining bases, the environmental impact of the military is now an important consideration in the operation of bases. Many previously-unknown environmental problems related to chemicals are surfacing. White phosphorus, a chemical commonly used as an obscurant, is a chemical previously thought to be innocuous after use. In 1990, however, it was linked to the deaths of thousands of waterfowl at the Eagle River Flats impact area on Ft Richardson near Anchorage, Alaska, USA, and shortly after, a series of remedial investigations was initiated. This paper describes three of the remedial methods currently under investigation, namely enhanced in-situ remediation, pond draining through ditching or pumping, and dredging. These three approaches are best applied in different environments, but they can be used together or in conjunction with other strategies. Their impacts on the environment will vary as well. Experience with these remediation strategies has proven very useful in determining the direction that the clean-up effort at Eagle River Flats (ERF) should take. Dredging, an effective means of removing contaminated sediments for off-site remediation, has been shown to be too slow and expensive at the ERF because unexploded ordnance is present. Enhanced natural remediation is effective under favourable climatological conditions in areas that experience intermittent flooding, but desaturation of the sediments is critical to its effectiveness. Pond draining by blasting a ditch effectively removes waterfowl feeding habitat, but attenuation of the contaminant is inhibited because the ditch increases flooding frequency, and the habitat alteration is permanent. Pond pumping, where feasible, has shown great potential for the desaturating of wide areas of ERF, enabling the natural attenuation mechanism to progress. Further investigation will be necessary to confirm these initial conclusions and determine the overall effectiveness of all three methodologies. Methods developed over the course of this work may be applied to other remediation projects where in-situ volatilization can occur and limited disturbance of wetlands is critical.

Measuring Energetic Contaminant Deposition Rates on Snow

Energetic residues from military live-fire training will accumulate on ranges and lead to the contamination of soil and water. Characterizing surface soils for energetic contamination has been conducted extensively in the past. However, deriving mass deposition rates on soils for specific munition-related activities, necessary for determining the cumulative impact of these activities and developing range sustainability models, has been problematic. Factors include determining the energetic residues deposition area, discriminating current deposition from previous activities, separating the residues from the collection matrix, and processing the samples. To circumvent these problems, methods were developed for sampling energetic residues on clean snow surfaces. At firing points, a clean snow surface allows the collection of propellant residues from a known quantity and type of munition. Explosives residues from projectile detonations can be sampled from clean snow- and ice-covered surfaces in active impact areas. Sampling protocols have been optimized and quality assurance procedures have been developed during years of research on munition residues deposition rates. These methods are currently being used in the US, Canada, and Norway for both energetics and metal contaminants with other applications under consideration. This paper describes the current sampling protocol for clean snow surfaces and presents examples of its application.

Subsampling of Soils Containing Energetics Residues

There are many sources of error on the path from field sample acquisition to subsample analysis. This paper examines one potential source, the subsampling of a processed field sample. Five archived ground field samples were subsampled to determine the optimal number of increments to construct a 10-g subsample. Bulk samples ranged from 338 g to 2150 g. The analytes were energetic compounds: crystalline, easy-to-grind explosives and difficult-to-grind propellants in a nitrocellulose matrix. A two-phase study was conducted with moderately high concentration samples and low concentration samples of each type of analyte. All samples were ground with a puck mill according to EPA method 8330B and analyzed on liquid chromatography instrumentation. Up to 40 increments were used to build each subsample and seven replicates executed for each test. Results demonstrate that for a well-ground and mixed sample, a single 10 g subsample is sufficient. For triplicate subsamples, however, 20 to 40 increments will give a result much closer to the concentration of the bulk sample. To minimize overall error due to incomplete mixing, improper grinding, or very low concentrations, we recommend about 30 increments be taken over the complete sample to construct the subsample.

Controlled expedient disposal of excess gun propellant

The expedient field disposal of excess gun propellants on the ground is an integral part of live-fire training in many countries. However, burning excess propellant in the field will leave significant quantities of energetic residues and heavy metals in the environment. Compounds such as dinitrotoluene and nitroglycerin and metals such as lead will leach into the soil column, eventually migrating to groundwater. Contamination of the environment will lead to high remediation costs and the possible loss of the training facility. After investigating the contamination at several propellant disposal sites, a portable propellant burn pan was developed and tested. The pan was transported to training sites where excess propellant was loaded and burned in a controlled manner. Up to 120 kg of excess single-base propellant charges have been burned during two series of tests at a consumption rate of greater than 99.9%. Less than 0.03% of the energetic material was recovered outside the burn pan. Recovered lead is largely contained within the pan. The turnover rate for burns is 15 min. The residues can be collected following cool-down for proper disposal.

Explosive particle soil surface dispersion model for detonated military munitions

The accumulation of high explosive mass residue from the detonation of military munitions on training ranges is of environmental concern because of its potential to contaminate the soil, surface water, and groundwater. The US Department of Defense wants to quantify, understand, and remediate high explosive mass residue loadings that might be observed on active firing ranges. Previously, efforts using various sampling methods and techniques have resulted in limited success, due in part to the complicated dispersion pattern of the explosive particle residues upon detonation. In our efforts to simulate particle dispersal for high- and low-order explosions on hypothetical firing ranges, we use experimental particle data from detonations of munitions from a 155-mm howitzer, which are common military munitions. The mass loadings resulting from these simulations provide a previously unattained level of detail to quantify the explosive residue source-term for use in soil and water transport models. In addition, the resulting particle placements can be used to test, validate, and optimize particle sampling methods and statistical models as applied to firing ranges. Although the presented results are for a hypothetical 155-mm howitzer firing range, the method can be used for other munition types once the explosive particle characteristics are known.

White Phosphorus Contamination of an Active Army Training Range

Detonations of military ordnance will leave various amounts of chemical residue on training ranges. Significant adverse ecological effects from these residues have not been documented except for ordnance containing white phosphorus. At a military training range in Alaska, USA, the deaths of thousands of waterfowl due to poisoning from white phosphorus ordnance prompted a two-decade-long investigation of the extent of the contamination, remediation technologies, and methods to assess and monitor the effectiveness of the remediation. This paper gives an overview of these investigations and provides the outcome of the remediation efforts.