Laser-induced breakdown spectroscopy for detection of explosives residues: a review of recent advances, challenges, and future prospects.

In this review we discuss the application of laser-induced breakdown spectroscopy (LIBS) to the problem of detection of residues of explosives. Research in this area presented in open literature is reviewed. Both laboratory and field-tested standoff LIBS instruments have been used to detect explosive materials. Recent advances in instrumentation and data analysis techniques are discussed, including the use of double-pulse LIBS to reduce air entrainment in the analytical plasma and the application of advanced chemometric techniques such as partial least-squares discriminant analysis to discriminate between residues of explosives and non-explosives on various surfaces. A number of challenges associated with detection of explosives residues using LIBS have been identified, along with their possible solutions. Several groups have investigated methods for improving the sensitivity and selectivity of LIBS for detection of explosives, including the use of femtosecond-pulse lasers, supplemental enhancement of the laser-induced plasma emission, and complementary orthogonal techniques. Despite the associated challenges, researchers have demonstrated the tremendous potential of LIBS for real-time detection of explosives residues at standoff distances.

Standoff detection of chemical and biological threats using laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) is a promising technique for real-time chemical and biological warfare agent detection in the field. We have demonstrated the detection and discrimination of the biological warfare agent surrogates Bacillus subtilis (BG) (2% false negatives, 0% false positives) and ovalbumin (0% false negatives, 1% false positives) at 20 meters using standoff laser-induced breakdown spectroscopy (ST-LIBS) and linear correlation. Unknown interferent samples (not included in the model), samples on different substrates, and mixtures of BG and Arizona road dust have been classified with reasonable success using partial least squares discriminant analysis (PLS-DA). A few of the samples tested such as the soot (not included in the model) and the 25% BG:75% dust mixture resulted in a significant number of false positives or false negatives, respectively. Our preliminary results indicate that while LIBS is able to discriminate biomaterials with similar elemental compositions at standoff distances based on differences in key intensity ratios, further work is needed to reduce the number of false positives/negatives by refining the PLS-DA model to include a sufficient range of material classes and carefully selecting a detection threshold. In addition, we have demonstrated that LIBS can distinguish five different organophosphate nerve agent simulants at 20 meters, despite their similar stoichiometric formulas. Finally, a combined PLS-DA model for chemical, biological, and explosives detection using a single ST-LIBS sensor has been developed in order to demonstrate the potential of standoff LIBS for universal hazardous materials detection.

Multivariate analysis of standoff laser-induced breakdown spectroscopy spectra for classification of explosive-containing residues.

A technique being evaluated for standoff explosives detection is laser-induced breakdown spectroscopy (LIBS). LIBS is a real-time sensor technology that uses components that can be configured into a ruggedized standoff instrument. The U.S. Army Research Laboratory has been coupling standoff LIBS spectra with chemometrics for several years now in order to discriminate between explosives and nonexplosives. We have investigated the use of partial least squares discriminant analysis (PLS-DA) for explosives detection. We have extended our study of PLS-DA to more complex sample types, including binary mixtures, different types of explosives, and samples not included in the model. We demonstrate the importance of building the PLS-DA model by iteratively testing it against sample test sets. Independent test sets are used to test the robustness of the final model.

Detection of indoor biological hazards using the man-portable laser induced breakdown spectrometer.

The performance of a man-portable laser induced breakdown spectrometer was evaluated for the detection of biological powders on indoor office surfaces and wipe materials. Identification of pure unknown powders was performed by comparing against a library of spectra containing biological agent surrogates and confusant materials, such as dusts, diesel soot, natural and artificial sweeteners, and drink powders, using linear correlation analysis. Simple models constructed using a second technique, partial least squares discriminant analysis, successfully identified Bacillus subtilis (BG) spores on wipe materials and office surfaces. Furthermore, these models were able to identify BG on materials not used in the training of the model.

Laser-induced breakdown spectroscopy for the classification of unknown powders.

Laser-induced breakdown spectroscopy (LIBS) was used to discern between two biological agent surrogates (Bacillus atrophaeus and ovalbumin) and potential interferent compounds (mold spores, humic acid, house dust, and Arizona road dust). Multiple linear regression and neural network analysis models were constructed by using B. atrophaeus and ovalbumin spectra, and limits of detection were calculated. Classification of the agent surrogates' LIBS spectra was attempted by using a neural network model. False negative rates of 0% were observed for B. atrophaeus (100 colony forming units) spore spectra with the neural network model used for classification.

On the behavior of indole-containing species sequestered within reverse micelles at sub-zero temperatures.

We report on the effects of temperature (+30 to -100 degrees C) on the fluorescence from N-acetyl tryptophanamide (NATA) and human serum albumin (HSA) sequestered within Aerosol-OT (AOT) reversed micelles. NATA reports simultaneously from the polar and non-polar side of the reverse micelle interface. As the sample temperature decreases, the relative fraction of NATA molecules associated with the polar side increases. This redistribution process is characterized by DeltaH = -14.8 +/- 0.6 kJ/mol and DeltaS = -54 +/- 2 J/(K mol). The activation energy for thermal quenching (E(a,TQ)) associated with the polar side NATA molecules is 6.7 kJ/mol before the micelles have shed water and 1.0 kJ/mol after water shedding (below approximately -20 degrees C). The time-resolved fluorescence intensity decay for tryptophan-214 in HSA is triple exponential. We suggest that these lifetimes arise from three indole residue conformations in equilibrium. Cooling the sample causes a freezing-in of the least quenched conformer; the other conformers are frozen out. The E(a,TQ) value for the shortest lifetime component is 6 kJ/mol. The E(a,TQ) for the long and intermediate lifetime components are equivalent (approximately 1.5 kJ/mol).

The local microenvironment surrounding dansyl molecules attached to controlled pore glass in pure and alcohol-modified supercritical carbon dioxide.

We report on the local microenvironment surrounding a free dansyl probe, dansyl attached to controlled pore glass (D-CPG), and dansyl molecules attached to trimethylsilyl-capped CPG (capped D-CPG) in pure and alcohol-modified supercritical CO2. These systems were selected to provide insights into the local microenvironment surrounding a reactive agent immobilized at a silica surface in contact with pure and cosolvent-modified supercritical CO2. Local surface-bound dansyl molecule solvation on the CPG surface depends on the dansyl molecule surface loading, the surface chemistry (uncapped versus capped), the bulk fluid density, and the alcohol gas phase absolute acidity. At high dansyl loadings, the surface-bound dansyl molecules are largely "solvated" by other dansyl molecules and these molecules are not affected significantly by the fluid phase. When the dansyl surface loading decreases, dansyl molecules can be accessed/solvated/wetted by the fluid phase. However, at the lowest dansyl loadings studied, the dansyl molecules are in a fluid inaccessible/restrictive environment and do not sense the fluid phase to any significant degree. In uncapped D-CPG, one can poise the system such that the local concentration of an environmentally less responsible cosolvent (alcohol) in the immediate vicinity of surface-immobilized dansyl molecules can approach 100% even though the bulk solution contains orders of magnitude less of this less environmentally responsible cosolvent. In capped C-CPG, the surface excess is attenuated in comparison to that of uncapped D-CPG. The extent of this cosolvent surface excess is discussed in terms of the dansyl surface loading, the local density fluctuations, the cosolvent and surface silanol gas phase acidities, and the silica surface chemistry. These results also have implications for cleanings, extractions, heterogeneous reactions, separations, and nanomaterial fabrication using supercritical fluids.

Temporal evolution of the laser-induced breakdown spectroscopy spectrum of aluminum metal in different bath gases.

The spectral emission of gas-phase aluminum and aluminum oxide was measured during and immediately after exposure of a bulk-aluminum sample to a laser-induced spark produced by a focused, pulsed laser beam (Nd:YAG, 10-ns pulse duration, 35 mJ/pulse, lambda = 1064 nm). The spectral emission was measured as a function of time after the onset of the laser pulse, and it was also measured in different bath gases (air, nitrogen, oxygen, and helium).

Dansylated aminopropyl controlled pore glass: a model for silica-liquid solvation.

We have prepared a series of aminopropyl controlled pore glass (CPG) particles that have been labeled with a solvatochromic fluorescent probe molecule (dansyl). We report on the behavior of the attached dansyl reporter as a function of dansyl-to-amine molar ratio (i.e., dansyl loading), solvent dipolarity, and surface-residue end capping. In these experiments, we systematically adjust the dansyl loading by 10(5); a range much larger than ever explored. The dansylated CPG particles were also end capped with trimethylchlorosilane to derivatize most of the residual silanol and/or aminopropyl groups. The attached dansyl molecules can be surrounded by other dansyl molecules; they can be distributed within an ensemble of sites with differing physicochemical properties, and/or they can be distributed in sites that are restrictive to dansyl motion and/or solvent inaccessible. At high dansyl loadings, the majority of the dansyl groups are solvated by other dansyl moieties and solvent does not significantly alter the local microenvironment surrounding the average dansyl molecule (i.e., the cybotactic region) to any significant level. At intermediate dansyl loadings, the average distance between the dansyl groups increases and solvent is able to access/solvate/wet the dansyl groups and alter their cybotactic region to a greater extent. At the lowest dansyl loadings studied, the results suggest that these dansyl moieties are localized within solvent inaccessible/restrictive SiO2 sites (e.g., small pores).