The existence of explosive related chemicals (ERCs) near the soil-atmospheric and other surfaces depend
on their fate and transport characteristics within the environmental settings. Consequently, detection of
ERC in environmental matrices is influenced by conditions that affect their fate and transport. Experimental
work to study the fate and transport behavior of ERCs relies on proper temporal and spatial sampling
techniques. Because the low vapor pressure of these chemicals and their susceptibility to adsorption and
degradation, vapor concentrations in environmental matrices are very low. Depending on the environmental
conditions, the amount of samples that can be withdrawn for analysis is also limited. It is, therefore,
necessary to develop sampling technologies that can provide quantitative measures of ERC concentrations
in limited sampling environments.
This paper presents experimental work conducted to develop a sampling technique to quantify DNT and
TNT vapor concentrations of low vapor-pressure ERCs in environmental setting having limited sampling
volumes and large sample numbers. Two potential vapor sampling techniques, Solid phase Microextraction
(SPME) and Solid Phase Extraction (SPE), were developed and evaluated. SPME sampling techniques are
excellent to quantify for DNT and TNT at very low concentrations. Its passive sampling capabilities meet
the requirement for low-volume environmental sampling, but measured concentrations may be lagged in
time. SPMEs' requirements for immediate analysis after sampling limit the technique for continuous vapor
sampling.
SPE showed to be a sensitive and reproducible technique to determine vapor concentrations of TNT and
DNT in atmospheric and soil setting having limited sampling volumes and large sample numbers. Smallvolume
(600&mgr;L) air samples provide measurements in the &mgr;gL-1 concentration range using isoamyl acetate
and acetonitrile as the solvents. Small extraction volumes make this technique cost efficient and attractive.
Issues with extraction inefficiencies, however, were observed and are being investigated.
Chemical detection of buried explosives devices (BEDs) through chemical sensing is influenced by factors affecting the transport
of chemical components associated with the devices. Explosive-related chemicals, such as 2,4-dinitrotolune (DNT), are
somewhat volatile and their overall transport is influenced by vapor-phase diffusion. Gaseous diffusion depends on
environmental and soil conditions. The significance of this mechanism is greater for unsaturated soil, and increases as water
content decreases. Other mechanisms, such as sorption and degradation, which affect the overall fate and transport, may be more
significant under diffusion transport due to the higher residence time of ERCs in the soil system. Gaseous diffusion in soil was
measured using a one-dimensional physical model (1-D column) to simulate the diffusion flux through soil under various
environmental conditions. Samples are obtained from the column using solid phase microextraction (SPME) and analyzed with a
gas chromatography. Results suggest that DNT overall diffusion is influenced by diffusive and retention processes, water content,
source characteristics, and temperature. DNT effective gas phase diffusion in the soil decreases with increasing soil water
content. Vapor transport retardation was more dominant at low water contents. Most of the retardation is associated to the
partition of the vapor to the soil-water. DNT vapor flux is higher near the explosive source (mine) than at the soil surface. This
flux also increases with higher soil water content and temperature. Results also suggest non-equilibrium transport attributed to
mass transfer limitations and non-linear sorption.
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