Deborah R. Felt

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.

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 (Bartletts and Levenes 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.

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 soils 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 shots surface was associated with increased W dissolution, compared to controls, following a simulated 1 year soil aging.

An extraction/concentration procedure for analysis of low-level explosives in soils

The methods traditionally used for explosives analysis in soil matrices have inherent data quality limitations for low-level samples. The traditional methods employ a soil-dilution extraction of the sample prior to analysis by high performance liquid chromatography with UV absorption detection. Another concern with the traditional analysis is that energetics contamination in environmental samples is often very heterogeneous in nature, usually requiring a large number of samples and multiple testing. The technique presented here addresses these data quality limitations by using a concentrative extraction procedure which produces a small volume of extract from a large soil sample. A concentration factor of 60-fold is achieved in this manner and energetics detection limits for soils are lowered by two orders of magnitude. The larger soil sample size also helps reduce the error associated with sample heterogeneity. The ability to detect explosive-based contaminants at levels of environmental interest enables a more accurate assessment of the transport pathways and treatment options for explosives contamination.

Hydrated lime for metals immobilization and explosives transformation:Treatability study

Fragmentation grenades contain Composition B (RDX and TNT) within a steel shell casing. There is the potential for off-site migration of high explosives and metals from hand grenade training ranges by transport in surface water and subsurface transport in leachate. This treatability study used bench-scale columns and mesocosm-scale laboratory lysimeters to investigate the potential of hydrated lime as a soil amendment for in situ remediation of explosives and metals stabilization in hand grenade range soils. Compared to the unamended soil there was a 26-92% reduction of RDX in the leachate and runoff water from the lime treated soils and a 66-83% reduction of zinc in the leachate and runoff water samples; where the hand grenade range metals of concern were zinc, iron, and manganese. The amended soil was maintained at the target pH of greater than 10.5 for optimum explosives decomposition. The treatability study indicated a high potential of success for scale-up to an in situ field study.

Solid-Phase Tungsten Speciation by Differential Digestion

In this study, a series of chemical extractions was used as a low-level, solid-phase tungsten speciation technique and correlated with XRD results. In addition to qualitative speciation, these efforts, which utilize the varying solubilities of WO−2 4, WO3, and W, provide statistically representative quantitative data at environmentally relevant levels. The selective nature of the digestion procedures allowed calculation of each individual species concentration by subtracting recoveries of the composite matrices from the total tungsten determinations. The results of this method exceed the sensitivity limitations of non-destructive techniques and may provide a valuable tool in environmental forensic investigations regarding the source of tungsten contamination.