Photo-induced enhanced Raman spectroscopy for universal ultra-trace detection of explosives, pollutants and biomolecules.

Surface-enhanced Raman spectroscopy is one of the most sensitive spectroscopic techniques available, with single-molecule detection possible on a range of noble-metal substrates. It is widely used to detect molecules that have a strong Raman response at very low concentrations. Here we present photo-induced-enhanced Raman spectroscopy, where the combination of plasmonic nanoparticles with a photo-activated substrate gives rise to large signal enhancement (an order of magnitude) for a wide range of small molecules, even those with a typically low Raman cross-section. We show that the induced chemical enhancement is due to increased electron density at the noble-metal nanoparticles, and demonstrate the universality of this system with explosives, biomolecules and organic dyes, at trace levels. Our substrates are also easy to fabricate, self-cleaning and reusable.

The spatial distribution patterns of condensed phase post-blast explosive residues formed during detonation.

The continued usage of explosive devices, as well as the ever growing threat of 'dirty' bombs necessitates a comprehensive understanding of particle dispersal during detonation events in order to develop effectual methods for targeting explosive and/or additive remediation efforts. Herein, the distribution of explosive analytes from controlled detonations of aluminised ammonium nitrate and an RDX-based explosive composition were established by systematically sampling sites positioned around each firing. This is the first experimental study to produce evidence that the post-blast residue mass can distribute according to an approximate inverse-square law model, while also demonstrating for the first time that distribution trends can vary depending on individual analytes. Furthermore, by incorporating blast-wave overpressure measurements, high-speed imaging for fireball volume recordings, and monitoring of environmental conditions, it was determined that the principle factor affecting all analyte dispersals was the wind direction, with other factors affecting specific analytes to varying degrees. The dispersal mechanism for explosive residue is primarily the smoke cloud, a finding which in itself has wider impacts on the environment and fundamental detonation theory.

Morphological Variations of Explosive Residue Particles and Implications for Understanding Detonation Mechanisms.

The possibility of recovering undetonated explosive residues following detonation events is well-known; however, the morphology and chemical identity of these condensed phase postblast particles remains undetermined. An understanding of the postblast explosive particle morphology would provide vital information during forensic examinations, allowing rapid initial indication of the explosive material to be microscopically determined prior to any chemical analyses and thereby saving time and resources at the crucial stage of an investigation. In this study, condensed phase particles collected from around the detonations of aluminized ammonium nitrate and RDX-based explosive charges were collected in a novel manner utilizing SEM stubs. By incorporating the use of a focused ion beam during analysis, for the first time it is possible to determine that such particles have characteristic shapes, sizes, and internal structures depending on the explosive and the distance from the detonation at which the particles are recovered. Spheroidal particles (10-210 µm) with microsurface features recovered following inorganic charge detonations were dissimilar to the irregularly shaped particles (5-100 µm) recovered following organic charge firings. Confirmatory analysis to conclude that the particles were indeed explosive included HPLC-MS, Raman spectroscopy, and mega-electron volt-secondary ionization mass spectrometry. These results may impact not only forensic investigations but also the theoretical constructs that govern detonation theory by indicating the potential mechanisms by which these particles survive and how they vary between the different explosive types.

The spatial distribution of postblast RDX residue: forensic implications.

Locating exactly where trace explosive residue samples should be sought during sample collection at bomb scenes is not specified in the published literature or guidelines; in this area, it is generally acknowledged that forensic practices are based on tradition rather than evidence. This study investigated patterns in the spatial distribution of postblast 1,3,5-trinitro-1,3,5-triazocyclohexane residue from a series of unconfined detonations, over a range of sampling sites, and at two different detonation heights. The amount of residue recovered from the sites decreased as a function of distance from the center of the explosion. [Correction added after online publication 27 December 2012: In the preceding sentence, "increased" was corrected to "decreased" to agree with the conclusion of the article.] As the height of the detonations increased, more residues were found from all sampling sites. The findings of this empirical study have a number of important practical implications including determining where residue samples are best sought at crime scenes.