A two-stage extraction procedure for insensitive munition (IM) explosive compounds in soils.

The Department of Defense (DoD) is developing a new category of insensitive munitions (IMs) that are more resistant to detonation or promulgation from external stimuli than traditional munition formulations. The new explosive constituent compounds are 2,4-dinitroanisole (DNAN), nitroguanidine (NQ), and nitrotriazolone (NTO). The production and use of IM formulations may result in interaction of IM component compounds with soil. The chemical properties of these IM compounds present unique challenges for extraction from environmental matrices such as soil. A two-stage extraction procedure was developed and tested using several soil types amended with known concentrations of IM compounds. This procedure incorporates both an acidified phase and an organic phase to account for the chemical properties of the IM compounds. The method detection limits (MDLs) for all IM compounds in all soil types were <5 mg/kg and met non-regulatory risk-based Regional Screening Level (RSL) criteria for soil proposed by the U.S. Army Public Health Center. At defined environmentally relevant concentrations, the average recovery of each IM compound in each soil type was consistent and greater than 85%. The two-stage extraction method decreased the influence of soil composition on IM compound recovery. UV analysis of NTO established an isosbestic point based on varied pH at a detection wavelength of 341 nm. The two-stage soil extraction method is equally effective for traditional munition compounds, a potentially important point when examining soils exposed to both traditional and insensitive munitions.

Relationship of surface changes to metal leaching from tungsten composite shot exposed to three different soil types.

Physical changes that occur on the surface of fired shots due to firing and impact with soil may increase the dissolution of muniton metals. Increased metal dissolution could potentially increase metal transport and leaching, affecting metal concentrations in surface and groundwater. This research describes the relationship between the surface changes on fired tungsten-nickel-iron (94% W:2% Ni:4% Fe) composite shots and metals leaching from those shots. Tungsten composite shot was fired into, and aged in, three soil types (Silty Sand, Sandy Clay, and Silt) in mesoscale rainfall lysimeters to simulate live-fire conditions and subsequent interactions between the metals of the composite and soil. Leachate, runoff, and soil samples were collected from the lysimeters and analyzed for metal content. The shots were analyzed using scanning electron microscopy (SEM) to evaluate surface changes. SEM results indicated that a soil's particle size distribution initially affected the amount of metal that was sheared from the surface of the fired W-composite shots. Shearing was greatest in soils with larger soil particles (sand and gravel); shearing was least in soils composed of small soil particles (fines). Increased metallic shearing from the shot's surface was associated with increased W dissolution, compared to controls, following a simulated 1 year soil aging.

The effects of grinding methods on metals concentrations in soil.

Multi-increment sampling (MIS) has been most extensively used for munitions constituents at environmental sites where a high degree of contaminant heterogeneity exits. A revised method (USEPA Method 8330B) for explosives that uses MIS was announced in the fall of 2006, but similar guidance has not been reported for testing metals in soils. Questions have been raised as how to prepare representative analytical samples for metals determination from field composites. Three different grinding procedures were used in this study for three soil types to determine if grinding (relative to homogenizing soil without grinding) increases metal concentrations and decreases variability. The performance of these procedures was demonstrated via the analysis of replicates (n=16 for two soil types) using statistical evaluations that included calculations of various descriptive statistics (e.g., medians, means and standard deviations), Kruskal-Wallis (KW) tests for the medians and two tests for the variances (Bartlett's and Levene's test). There was a slight increase in concentrations for several of the metals in the clay loam soil after grinding, although the increases were a small percentage of the concentrations measured. The standard deviations (and variances) for replicate digestions and analyses generally decreased, although anomalies were observed. The grinding methods increased precision overall, however, the data indicated that the roller mill grinding was not as effective as the other grinding methods tested.

UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction.

Contamination of groundwater, surface water and soil by explosives has occurred at military sites throughout the world as a result of manufacture of explosive compounds, assembly of munitions, and deployment of explosives containing devices. Due to the adverse effects of explosives on humans and other natural receptors, a low cost means of decontaminating these areas of contamination is needed. Base-induced transformation of explosives has shown promise as a rapid, low cost, and minimally resource-intensive technology for detoxifying explosives in soil and water. In order to understand the reaction mechanism, a reaction mixture of 2:1:1 (water:2,4,6-trinitrotoluene (TNT):1 N KOH) was analyzed by UV/VIS spectrometry from 190 to 1,100 nm. Time course measurements were conducted at 25, 20, 15, and 12 degrees C. A factor analysis program was used to analyze the spectral data. Principal component analysis indicated that six principal components explained the spectra to within experimental error, with four factors explaining the majority of the variance. Test spectral vectors for four components were developed, including TNT, two intermediates, and the final product, and were tested against the abstract vectors. Two possible reaction mechanisms were suggested and tested to explain the spectral data.

Analysis of CL-20 in environmental matrices: water and soil.

Analytical techniques for the detection of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo(5.5.0.05,9.03,11)dodecane (CL-20) in water and soil are developed by adapting methods traditionally used for the analysis of nitroaromatics. CL-20 (a new explosives compound) is thermally labile, exhibits high polarity, and has low solubility in water. These constraints make the use of specialized sample handling, preparation, extraction, and analysis necessary. The ability to determine the concentrations of this new explosive compound in environmental matrices is helpful in understanding the environmental fate and effects of CL-20; understanding the physical, chemical, and biological fate of CL-20; and can be used in developing remediation technologies and determining their efficiency. The toxicity and mobility of new explosives in soil and groundwater are also of interest, and analytical techniques for quantitating CL-20 and its degradation products in soil and natural waters make these investigations possible.