Félix Zapata

Detection and identification of explosives by surface enhanced Raman scattering

ABSTRACT Surface Enhanced Raman Scattering (SERS) has undergone an important development over the last few years, particularly in the detection and identification of extremely low traces of explosives. The large number of studies and results generated by this increasing research makes a comprehensive overview necessary. This work reviews in detail that research focused on the identification of explosives by SERS, including TNT, DNT, RDX, PETN, TATP, HMTD, perchlorate, etc. either in bulk state, in solution or in vapor phase. In brief, TNT and DNT have been widely studied by SERS due to its aromatic structure and LODs down to 5–10 zg and 10−17–10−13 M have been achieved. The other explosives have been quite less researched; therefore, few results are available to be compared and a bit more modest LODs have been reached such as 10−13 M for RDX, 10−4 M for TATP, 5 pg for PETN, or 10−9 M for perchlorate. In addition, the challenges of detecting both explosives vapors and perchlorate anion by SERS are thoroughly discussed.

Progressing the analysis of Improvised Explosive Devices: Comparative study for trace detection of explosive residues in handprints by Raman spectroscopy and liquid chromatography

Concerning the dreadful global threat of terrorist attacks, the detection of explosive residues in biological traces and marks is a current need in both forensics and homeland security. This study examines the potential of Raman microscopy in comparison to liquid chromatography (ion chromatography (IC) and reversed-phase high performance liquid chromatography (RP-HPLC)) to detect, identify and quantify residues in human handmarks of explosives and energetic salts commonly used to manufacture Improvised Explosive Devices (IEDs) including dynamite, ammonium nitrate, single- and double-smokeless gunpowders and black powder. Dynamite, ammonium nitrate and black powder were detected through the identification of the energetic salts by Raman spectroscopy, their respective anions by IC, and organic components by RP-HPLC. Smokeless gunpowders were not detected, either by Raman spectroscopy or the two liquid chromatography techniques. Several aspects of handprint collection, sample treatment and a critical comparison of the identification of compounds by both techniques are discussed. Raman microscopy and liquid chromatography were shown to be complementary to one another offering more comprehensive information for trace explosives analysis.

Determination of Nanogram Microparticles from Explosives after Real Open-Air Explosions by Confocal Raman Microscopy

Explosives are increasingly being used for terrorist attacks to cause devastating explosions. The detection of their postblast residues after an explosion is a high challenge, which has been barely investigated, particularly using spectroscopic techniques. In this research, a novel methodology using confocal Raman microscopy has been developed for the analysis of postblast residues from 10 open-air explosions caused by 10 different explosives (TNT, RDX, PETN, TATP, HMTD, dynamite, black powder, ANFO, chloratite, and ammonal) commonly used in improvised explosive devices. The methodology for the determination of postblast particles from explosives consisted of examining the samples surfaces with both the naked eye, first, and microscopically (10× and 50×), immediately afterward; and finally, analyzing the selected residues by confocal Raman spectroscopy in order to identify the postblast particles from explosives. Interestingly, confocal Raman microscopy has demonstrated to be highly suitable to rapidly, selectively, and noninvasively analyze postblast microscopic particles from explosives up to the nanogram range.

Study of consumer fireworks post-blast residues by ATR-FTIR

Specific analytical procedures are requested for the forensic analysis of pre- and post-blast consumer firework samples, which present significant challenges. Up to date, vibrational spectroscopic techniques such as Fourier transform infrared spectroscopy (FTIR) have not been tested for the analysis of post-blast residues in spite of their interesting strengths for the forensic field. Therefore, this work proposes a simple and fast procedure for the sampling and analysis of consumer firework post-blast residues by a portable FTIR instrument with an Attenuated Total Reflection (ATR) accessory. In addition, the post-blast residues spectra of several consumer fireworks were studied in order to achieve the identification of their original chemical compositions. Hence, this work analysed 22 standard reagents usually employed to make consumer fireworks, or because they are related to their combustion products. Then, 5 different consumer fireworks were exploded, and their residues were sampled with dry cotton swabs and directly analysed by ATR-FTIR. In addition, their pre-blast fuses and charges were also analysed in order to stablish a proper comparison. As a result, the identification of the original chemical compositions of the post-blast samples was obtained. Some of the compounds found were potassium chlorate, barium nitrate, potassium nitrate, potassium perchlorate or charcoal. An additional study involving chemometric tools found that the results might greatly depend on the swab head type used for the sampling, and its sampling efficiency. The proposed procedure could be used as a complementary technique for the analysis of consumer fireworks post-blast residues.

Body Fluids and Spectroscopic Techniques in Forensics: A Perfect Match?

Human body fluids are of great interest in forensics, due to the possibility to extract their genetic information. At the moment, there is the need to develop a non-destructive, rapid and user-friendly method for the detection and identification of the body fluids usually found at crime scenes: blood, semen, vaginal fluid, saliva, sweat and urine. In this review, the spectroscopic techniques used or being researched on this topic are discussed, taking into account their advantages, limitations and advances. Although, UV-Vis light sources are used worldwide in forensic laboratories for the location of body fluids, they are not selective enough to be confirmatory. HSI, FTIR and Raman spectroscopy seem to be suitable for the identification and discrimination of body fluids, though comprehensive research about some unsolved aspects must be performed first.

Differentiation of Body Fluid Stains on Fabrics Using External Reflection Fourier Transform Infrared Spectroscopy (FT-IR) and Chemometrics

Body fluids are evidence of great forensic interest due to the DNA extracted from them, which allows genetic identification of people. This study focuses on the discrimination among semen, vaginal fluid, and urine stains (main fluids in sexual crimes) placed on different colored cotton fabrics by external reflection Fourier transform infrared spectroscopy (FT-IR) combined with chemometrics. Semen–vaginal fluid mixtures and potential false positive substances commonly found in daily life such as soaps, milk, juices, and lotions were also studied. Results demonstrated that the IR spectral signature obtained for each body fluid allowed its identification and the correct classification of unknown stains by means of principal component analysis (PCA) and soft independent modeling of class analogy (SIMCA). Interestingly, results proved that these IR spectra did not show any bands due to the color of the fabric and no substance of those present in daily life which were analyzed, provided a false positive.

Analysis of human bodily fluids on superabsorbent pads by ATR-FTIR

Superabsorbent pads are composed of different layers with different grades of absorbent capacity, being the lower one the most absorbent layer. Due to their complexity, the analysis of bodily fluids on superabsorbent pads is certainly difficult. In this study, semen, vaginal fluid and urine stains placed on superabsorbent pads including sanitary napkins, panty-liners and diapers were non-destructively detected by Attenuated Total Reflectance (ATR) Fourier Transform Infrared spectroscopy (FTIR). In spite of the higher absorbent capacity of the lower layers, this technique was able to detect the three fluids on the upper layer of all pads, showing that bodily fluids are distributed within all layers. Additionally, mixtures of these bodily fluids prepared on superabsorbent pads and cotton were studied, since real forensic investigations involving sexual abuse cases usually deal with mixtures of these fluids. Due to their IR marked protein region (1800-1480cm-1), semen and vaginal fluid were easily distinguished from urine. However, since semen and vaginal fluid have both a high protein composition, that region of their IR signatures were quite similar, except for slight visual differences, that should be further analysed. Therefore, we propose ATR-FTIR as a suitable, presumptive, non-destructive and rapid approach to detect stains of human bodily fluids on the upper layer of superabsorbent pads from sexual crimes.

Revealing the location of semen, vaginal fluid and urine in stained evidence through near infrared chemical imaging

Crime scene investigation (CSI) requires the ultimate available technology for a rapid, non-destructive, and accurate detection of a wide variety of evidence including invisible stains of bodily fluids. Particularly crucial is the discrimination of semen in stained evidence from sexual abuse cases. This is because those evidence have high odds of containing the DNA from the aggressor. To this aim, we demonstrated the potential of near infrared hyperspectral imaging (NIR-HSI) to make visible stains of semen, vaginal fluid, and urine on fabrics, which lays the bases to face the challenging visualization and discrimination of semen within bodily fluids mixtures. Combining the NIR-HSI data and simple chemometric techniques such as principal component analysis and classical least squares regression, we have revealed the location of semen, vaginal fluid and urine in bodily fluids stained evidence.

Analysis of different materials subjected to open-air explosions in search of explosive traces by Raman microscopy

Post-explosion scenes offer such chaos and destruction that evidence recovery and detection of post-blast residues from the explosive in the surrounding materials is highly challenging and difficult. The suitability of materials to retain explosives residues and their subsequent analysis has been scarcely investigated. Particularly, the use of explosive mixtures containing inorganic oxidizing salts to make improvised explosive devices (IEDs) is a current security concern due to their wide availability and lax control. In this work, a wide variety of materials such as glass, steel, plywood, plastic bag, brick, cardboard or cotton subjected to open-air explosions were examined using confocal Raman microscopy, aiming to detect the inorganic oxidizing salts contained in explosives as black powder, chloratite, dynamite, ammonium nitrate fuel oil and ammonal. Post-blast residues were detected through microscopic examination of materials surfaces. In general, the more homogeneous and smoother the surface was, the less difficulties and better results in terms of identification were obtained. However, those highly irregular surfaces were the most unsuitable collectors for the posterior identification of explosive traces by Raman microscopy. The findings, difficulties and some recommendations related to the identification of post-blast particles in the different materials studied are thoroughly discussed.

The discrimination of 72 nitrate, chlorate and perchlorate salts using IR and Raman spectroscopy

Inorganic oxidizing energetic salts including nitrates, chlorates and perchlorates are widely used in the manufacture of not only licit pyrotechnic compositions, but also illicit homemade explosive mixtures. Their identification in forensic laboratories is usually accomplished by either capillary electrophoresis or ion chromatography, with the disadvantage of dissociating the salt into its ions. On the contrary, vibrational spectroscopy, including IR and Raman, enables the non-invasive identification of the salt, i.e. avoiding its dissociation. This study focuses on the discrimination of all nitrate, chlorate and perchlorate salts that are commercially available, using both Raman and IR spectroscopy, with the aim of testing whether every salt can be unequivocally identified. Besides the visual spectra comparison by assigning every band with the corresponding molecular vibrational mode, a statistical analysis based on Pearson correlation was performed to ensure an objective identification, either using Raman, IR or both. Positively, 25 salts (out of 72) were unequivocally identified using Raman, 30 salts when using IR and 44 when combining both techniques. Negatively, some salts were undistinguishable even using both techniques demonstrating there are some salts that provide very similar Raman and IR spectra.