Deep Ultra Violet Raman Spectroscopy (DUV-RS) is an emerging tool for vibrational spectroscopy analysis and can be used in Point Detection mode to detect explosive components of landmines and Improvised Explosive Devices (IED). Interactions of explosives with different substrates can be measured by using quantitative vibrational signal shift information of scattered Raman light associated with these interactions. In this research, grounds were laid for detection of explosives using UV-Raman Spectroscopy equipped with 244 nm laser excitation line from a 488 nm frequency doubled Coherent FreD laser. In other experiments, samples of 2,4-DNT were allowed to interact with Ottawa Sand and were studied using DUV-RS. Characteristic vibrational signals of energetic compounds were analyzed in the ranges: 400-1200 cm<sup>-1</sup>, 1200-1800 cm<sup>-1</sup>, and 2800-3500 cm<sup>-1</sup>. In addition these Raman spectra were compared with dispersive spectra that were acquired using Raman Microscopy equipped with 514.5 nm (VIS) 785 nm (NIR) and 1064 nm (NIR) excitation lasers.
Landmines have been a part of war technology for many years. As a result of the continued and indiscriminate use in approximately 90 countries landmines pose a severe and ever growing problem and a daily risk. Raman Spectroscopy is capable of providing rich information about the molecular structure of the sample and pinpoint detection of many chemicals, both of organic and inorganic nature. The presence of landmines in soils can be detected by Raman Spectroscopy sensing in a Point Detection modality, using characteristic vibrational signals of each explosive present in landmines. Detection of 2,4-DNT in sand and studies on how the vibrational signatures of 2,4-DNT is modified by interacting with soil particles and environmental conditions is reported. Raman Microspectrometers equipped with 514 nm and 785 nm laser excitation lines were used. The work focused in how the spectroscopic signatures of DNT in contact with Ottawa Sand are affected by the presence of humidity, pH, temperature, UV light and reaction times. Samples of mixtures of sand/2,4-DNT were analyzed by Raman Spectroscopy at 10, 50 and 100% water content and temperatures in range of 40-80 °C. Mixtures were also analyzed at different pH: 4, 7 and 10 and under ultraviolet light at 254 nm. Raman spectra were taken as a function of time in an interval from 24 to 336 hours (two weeks). Characteristic signals of 2,4-DNT were analyzed in different ranges 100-3800 cm<sup>-1</sup>, 600-1200 cm<sup>-1</sup>, 300-1700 cm<sup>-1</sup> and 2800-3500 cm<sup>-1</sup>. The effect of these variables was measured during 45 consecutive days. It was confirmed that the decrease of characteristic vibrational signatures of 2,4-DNT can be attributed to increase of the degradation of 2,4-DNT by the simulated environmental conditions. Spectroscopic characterization of degradation products, both in contact with sand as well as airborne is under way. These results will make possible the development of highly sensitive sensors for detection of explosives materials and correlated with their degradation products in landmines.
Surface Enhanced Raman Scattering (SERS) is normally obtained from nanoactive surfaces or colloids of group II-B metals, in particular of silver and gold. In this study another type of nanosurface has been explored seeking more reproducible Raman spectra than those obtained from metallic substrates. Compounds of elements of the fourth transition period were tested for SERS analysis of nitroexplosives. Titanium (IV) oxides were found to give good Raman Enhanced signals of target molecules. TNT and DNT increased their signal intensities for this technique and were evaluated for the increase in different excitation sources. Laser lines at 785, 532 and 514.5 nm were evaluated to determine relative SERS cross sections for various vibrational bands of the target nitroexplosives. Polymorphism seems to play an important role in the Raman signal enhancement when using metal oxides: high rutile percent mixtures with anatase gave higher Raman scattered signal enhancement.
TNT and DNT are important explosives used as base charges of landmines and other explosive devices. They are often combined with RDX in specific explosive formulations. Their detection in vapor phase as well as in soil in contact with the explosives is important in landmine detection technology. The spectroscopic signatures of nitroaromatic compounds in neat forms: crystals, droplets, and recrystallized samples were determined by Raman Microspectroscopy (RS), Fourier Transform Infrared Microscopy (FTIR) and Fiber Optics Coupled - Fourier Transform Infrared Spectroscopy (FOC-FTIR) using a grazing angle (GA) probe. TNT exhibits a series of characteristic bands: vibrational signatures, which allow its detection in soil. The spectroscopic signature of neat TNT is dominated by strong bands about 1380 and 2970 cm<sup>-1</sup>. The intensity and position of these bands were found remarkably different in soil samples spiked with TNT. The 1380 cm<sup>-1 </sup>band is split into a number of bands in that region. The 2970 cm<sup>-1 </sup>band is reduced in intensity and new bands are observed about 2880 cm<sup>-1</sup>. The results are consistent with a different chemical environment of TNT in soil as compared to neat TNT. Interactions were found to be dependent on the physical source of the explosive. In the case of DNT-sand interactions, shifts in vibrational frequencies of the explosives as well as the substrates were found.
Raman Spectroscopy is a well established tool for vibrational spectroscopy analysis. Interactions of explosives with different substrates can be measured by using quantitative vibrational signal shift information of scattered Raman light associated with these interactions. A vibrational spectroscopic study has been carried out on 2,4-DNT and 2,6-DNT crystals. Raman Microscopy spectrometers equipped with 514 nm and 785 nm laser excitation lines were used. The samples were recrystallized on different solvents (water, methanol and acetonitrile) and allowed to interact with soil samples. The interaction with sand and soil samples doped with the nitroaromatic compounds showed significant shifts in its peaks. The above information was used to detect DNT in soil using Raman Microscopy. These results will make possible the development of highly sensitive sensors for detection of explosives materials.
Nitrogen-rich compounds have a large cross section for resonance electron capture at very low incident electron energies. Although this fact has been known for a number of years, full benefit of this ubiquitous property of NOX compounds for explosives detection studies has not been fully implemented. Here we report detection of picogram to femtogram levels of TNT, 2,4-DNT and RDX in soil samples and other complex matrices. Toluene extracts as well as thermally desorbed GC-MS analyses were conducted using a JEOL GCmate II coupled to a Tunable-Energy Electron Monochromator (TEEM). Use of TEEM-GC/MS permitted rapid sweeping of electron energy and tuning of the electron monochromator and ion source while monitoring the electron capture resonance in real time. In addition, Solid-Phase Micro-Extraction (SPME) was used to selectively preconcentrate analytes prior conventional GC/MS analysis. The SPME protocol was able to screen explosives in spiked water, in concentrations below the reported detection limits. Standard solutions of TNT were prepared in the range of interest (0.5-10 ppm) and analyzed using a GC/MSD direct injection. Potential use of developed methodology in landmine environmental studies and sensors development will be discussed.