Accumulation of explosives in hair

The sorption of explosives (TNT, RDX, PETN, TATP, EGDN) to hair during exposure to their vapors is examined. Three colors of hair were simultaneously exposed to explosive vapor. Following exposure of hair, the sorbed explosive was removed by extraction with acetonitrile and quantified. Results show that sorption of explosives, via vapor diffusion, to black hair is significantly greater than to blond, brown or bleached hair. Furthermore, the rate of sorption is directly related to the vapor density of the explosive: EGDN > TATP >TNT > PETN > RDX. In some cases, the explosive-containing hair was subject to repeated washings with sodium dodecylsulfate or simply left out in an open area to determine the persistence of the explosive contamination. While explosive is removed from hair with time or washing, some persists. These results indicate that hair can be a useful indicator of explosive exposure/handling.     

Accumulation of explosives in hair--part II: factors affecting sorption

This study examines the sorption of eight explosives (2,4,6-trinitrotoluene [TNT]; pentaerythritol tetranitrate [PETN]; hexahydro-1,3,5-trinitro-s-triazine [RDX]; diacetone diperoxide [DADP]; triacetone triperoxide [TATP]; ethylene glycol [EGDN], nitroglycerin [NG]; and 2,4-dinitrotoluene [DNT]) to human hair. The study uses only cut hair, which is exposed to explosive vapor. The vapor transfer studies reported herein indicated that hair did not reach saturation even after 2.5 years of exposure to TNT. While previous studies showed black hair sorbed more explosive than blond or brown, this study reports that red hair sorption is similar to black, while grey hairs, exposed along with black hair from the same individual, sorbed significantly less explosive than the same individual's black hairs. In a study using only black hair, a slight racial bias was observed with sorption greater for Mongoloid hair as compared to Caucasian or Negroid. Only for Mongoloid hairs were enough samples studied to examine for a gender bias, but one was not observed. There was much variability in results in all categories (hair color, race, and gender) that trends were established only in general terms. Hair at different ages was tested for a few individuals. Detailed studies focused on the sorption of TATP and TNT as these appear to be sorbed most differently-TATP mainly on the hair surface and TNT both on the surface and in the cortex. The uptake of high vapor pressure explosives (e.g., TATP) and moderate vapor pressure explosives (e.g., TNT) by hair was rapid and could be detected within about 1 h of exposure. Both explosives were readily sorbed by pure melanin.     

Detection of explosives in hair using ion mobility spectrometry

Conventional explosives 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), and ethylene glycol dinitrate (EGDN) sorbed to hair can be directly detected by an ion mobility spectrometer (IMS) in E-mode (for explosives). Terrorist explosive, triacetone triperoxide (TATP), difficult to detect by IMS in E-mode, was detected in N-mode (for narcotics). Three modes of sample introduction to IMS vapor desorption unit were used: (i) placement of hair directly into the unit, (ii) swabbing of hair and placement of swabs (i.e., paper GE-IMS sample traps) into the unit, and (iii) acetonitrile extracts of hair positioned on sample traps and placed into the unit. TNT, NG, and EGDN were detected in E-mode by all three sample introduction methods. TATP could only be detected by the acetonitrile extraction method after exposure of the hair to vapor for 16 days because of lower sensitivity. With standard solutions, TATP detection in E-mode required about 10 times as much sample as EGDN (3.9 mug compared with 0.3 mug). IMS in N-mode detected TATP from hair by all three modes of sample introduction.     

Detection of nitro-organic and peroxide explosives in latent fingermarks by DART- and SALDI-TOF-mass spectrometry

The ability of two mass spectrometric methods, surface-assisted laser desorption/ionization-time of flight-mass spectrometry (SALDI-TOF-MS) and direct analysis in real time (DART-MS), to detect the presence of seven common explosives (six nitro-organic- and one peroxide-type) in spiked latent fingermarks has been examined. It was found that each explosive could be detected with nanogram sensitivity for marks resulting from direct finger contact with a glass probe by DART-MS or onto stainless steel target plates using SALDI-TOF-MS for marks pre-dusted with one type of commercial black magnetic powder. These explosives also could be detected in latent marks lifted from six common surfaces (paper, plastic bag, metal drinks can, wood laminate, adhesive tape and white ceramic tile) whereas no explosive could be detected in equivalent pre-dusted marks on the surface of a commercial lifting tape by the DART-MS method due to high background interference from the tape material. The presence of TNT and Tetryl could be detected in pre-dusted latent fingermarks on a commercial lifting tape for up to 29 days sealed and stored under ambient conditions.     

Accumulation of explosives in hair--Part 3: Binding site study

This study extends previous work on the sorption of explosives to the hair matrix. Specifically, we have studied the interaction of 2,4,6-trinitrotoluene (TNT) and triacetone triperoxide (TATP) as a function of chemical pretreatment with acetonitrile, neutral and alkaline hydrogen peroxide, methanolic KOH and potassium permanganate, and the morphological changes that accompany these treatments. While differences in vapor pressure can account for quantitative differences between TNT and TATP sorption, both are markedly affected by the chemical rinses. Examination of the hair surface shows different degrees of smoothening following rinsing, suggesting that the attachment to hair is largely a surface phenomenon involving the 18-methyleicosanoic acid lipid layer. Density functional theory calculations were employed to explore possible nucleation sites of TATP microcrystals on the hair. We conclude that some of the sites on melanin granular surfaces may support nucleation of TATP microcrystals. Moreover, the calculations support the experimental finding that dark hair adsorbs explosives better than light hair.     

An enzyme-linked immunosorbent assay (ELISA) for trinitrotoluene (TNT) residue on hands

An enzyme-linked immunosorbent assay (ELISA) developed for the detection of trinitrotoluene (TNT) in munitions wastewater has been adapted to the detection of TNT residue on hands following contact. Using the procedure developed, as little as 50 pg of TNT could be detected. Accounting for sample size and dilution, the 50 pg equates to 15 ng of TNT recovered from the hands. Following contact with TNT, amounts ranging from 53 ng to more than 1500 ng were recovered from hands. The monoclonal anti-TNT antibodies showed no cross-reactivity with several other explosives or common contaminants. These preliminary results indicate promise for the development of a simple-to-use, immunoassay-based field test kit for TNT and, ultimately, other explosives.     

Visual detection of trace nitroaromatic explosive residue using photoluminescent metallole-containing polymers

The detection of trace explosives is important for forensic, military, and homeland security applications. Detection of widely used nitroaromatic explosives (trinitrotoluene [TNT], 2,4-dinitrotoluene [DNT], picric acid [PA]) was carried out using photoluminescent metallole-containing polymers. The method of detection is through the quenching of fluorescence of thin films of the polymer, prepared by spray coating organic solutions of the polymer, by the explosive analyte. Visual quenching of luminescence (lambda(em) approximately 400-510 nm) in the presence of the explosive is seen immediately upon illumination with near-UV light (lambda(ex)=360 nm). Detection limits were observed to be as low as 5 ng for TNT, 20 ng for DNT, and 5 ng for PA. In addition, experiments with normal production line explosives and their components show that this technology is also able to detect composition B, Pyrodex, and nitromethane. This method offers a convenient and sensitive method of detection of trace nitroaromatic explosive residue.     

Detection of Contact Traces of Powdery Substances

The current practice in securing the contact traces of chemical substances taken from clothes belonging to a person suspected of manual handling explosives is focused on pockets and cuffs. The outerwear worn by people who had contact with fluorescent powders that simulate explosives and drugs was the subject of this study. Clothes were first exposed to the test substance for a period of time and then analyzed by fluorescence methods to determine the location of the highest quantity of traces. The results obtained from the study confirm that the areas with the highest concentration of powdery traces are different from those suggested by current forensic practice. They appear to be promising for a more efficient identification of the suspects involved in illegal manufacturing of drugs of abuse or explosives. Moreover, they may be helpful for developing the methodology for handling the evidence material in the forensic clothing examination process.     

Trends in explosive contamination

This study sought to assign a rough order of magnitude for the amount of explosive residue likely to be available in real-world searches for clandestine explosives. A variety of explosives (TNT, TATP, HMX, AN, RDX, PETN) in various forms (powder, flake, detonating cord, plastic) were carefully weighed or cut into containers, and the amount of residue inadvertently remaining on the work area, hands, or containers was quantified. This was used to evaluate the spillage potential of each explosive. The adhesion of each explosive to a glass surface was quantified from amount of explosive adhering to the inside of a glass vial into which the explosive had been placed and then removed by vigorous tapping. In powdered form, most of the explosives--TNT, PETN, RDX, HMX, and TATP--exhibited similar spillage and adhesion to glass. However, PETN as sheet explosive and plasticized RDX (C-4), showed very little potential to contaminate surfaces, either by spillage or adhesion to glass.     

Application of LC−QTOF/MS for the validation and determination of organic explosive residues on Ionscan® swabs

The identification and confirmation of trace explosive residues along with potential precursors and degradation products require a comprehensive laboratory analysis procedure. This study presents the determination of organic explosives consisting of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2,4,6,N-tetranitro-N-methylaniline (Tetryl), 1,3,5-trinitrobenzene (1,3,5-TNB) and pentaerythritol tetranitrate (PETN) by a high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC−QTOF/MS). The qualitative information including retention time, collision energy, precursor ions, and characteristic fragmentation pattern of each explosive were collected using an atmospheric pressure chemical ionization (APCI) in negative ion mode. The separation efficiency among five compounds was greatly achieved in this study. Four real explosive samples consisting of TNT, RDX, PETN and Tetryl and 12 Ionscan® quality control swabs from the Royal Thai Army were also tested to validate and verify the viability of the GC–MS method used to validate results from an Ionscan® system. The results showed that LC−QTOF/MS is a powerful technique for the identification and confirmation of thermally unstable organic explosives on Ionscan® swabs compared to a conventional GC−MS technique.     

Selective detection of trace nitroaromatic, nitramine, and nitrate ester explosive residues using a three-step fluorimetric sensing process: a tandem turn-off, turn-on sensor

Detection of trace quantities of explosive residues plays a key role in military, civilian, and counter-terrorism applications. To advance explosives sensor technology, current methods will need to become cheaper and portable while maintaining sensitivity and selectivity. The detection of common explosives including trinitrotoluene (TNT), cyclotrimethylenetrinitramine, cyclotetramethylene-tetranitramine, pentaerythritol tetranitrate, 2,4,6-trinitrophenyl-N-methylnitramine, and trinitroglycerin may be carried out using a three-step process combining "turn-off" and "turn-on" fluorimetric sensing. This process first detects nitroaromatic explosives by their quenching of green luminescence of polymetalloles (lambda em approximately 400-510 nm). The second step places down a thin film of 2,3-diaminonaphthalene (DAN) while "erasing" the polymetallole luminescence. The final step completes the reaction of the nitramines and/or nitrate esters with DAN resulting in the formation of a blue luminescent traizole complex (lambda(em) = 450 nm) providing a "turn-on" response for nitramine and nitrate ester-based explosives. Detection limits as low as 2 ng are observed. Solid-state detection of production line explosives demonstrates the applicability of this method to real world situations. This method offers a sensitive and selective detection process for a diverse group of the most common high explosives used in military and terrorist applications today.     

Rapid screening of selected organic explosives by high performance liquid chromatography using reversed-phase monolithic columns

This study presents the rapid screening of various high grade explosives by high performance liquid chromatography (HPLC) with monolithic stationary phases. Two gradient methods were developed, the first for quantitative analysis of eleven explosives: HMX; RDX; Tetryl; TNT; 2,3-DNT; 2,6-DNT; 3,4-DNT; 2-NT; 3-NT; 4-NT; and PETN in under 14 min. The second method separated seven explosives in under two min and is suitable for rapid screening to determine the presence of specific and/or class of explosive. The rapid screening methods were successfully applied to soils spiked with known amounts of target explosives. This technology showed excellent potential for forensic explosives detection and analysis.     

Recovery of DNA and fingermarks following deployment of render-safe tools for vehicle-borne improvised explosive devices (VBIED)

Improvised explosive devices (IED) are responsible for a significant proportion of combat and civilian deaths around the world. Given the ease with which IEDs can be made, the large quantity of explosive which can be contained within or on a vehicle, and the use of VBIED in the past (for example the 2002 Bali bombing) in terrorist activities, VBIED are an ongoing concern for Defence and law enforcement agencies. Fingermark and DNA analyses are routinely used by police and forensic analysts to identify suspects involved in illegal activities. There is limited information available on the feasibility of obtaining fingermarks, fibres, hair and DNA samples following an explosive incident, or a situation whereby an IED has been rendered safe following the utilisation of an appropriate defeat or render-safe tool. The main objective of this study was to determine if fingermarks and/or DNA (from saliva and hair samples) placed on the interior and exterior of road vehicles, and on inanimate objects (such as plastic or glass bottles), are able to be obtained and analysed following the use of a vehicle-borne IED (VBIED) render-safe tool on a vehicle containing simulated explosives. The identification of fingermarks on the exterior (67.2±8.5%) and interior (43.8±17.8%) of the vehicles was possible following the use of the render-safe tool, though this was more challenging in the latter than the former. Fingermarks were also able to be identified from both plastic and glass bottles placed inside the vehicles. Polymerase chain reaction (PCR) techniques yielded DNA profiles that were able to be identified from saliva and hair samples. These preliminary results suggest that both fingermarks and DNA profiles, obtained from vehicles that have been subjected to a VBIED render-safe tool, may be used to identify persons of interest.     

Rapid changes in profiles from stored materials used in scent training of explosive detection dogs

Canines trained on scents from materials emitting vapours of explosives and related compounds are widely used to detect explosives in civilian, military and forensic applications. Despite the importance of these training materials, there is limited knowledge on how long these subsamples can be stored and whether vapour profiles change over time. We developed a sampling methodology that makes use of a secondary chamber for stabilisation of headspace concentration to allow reliable and reproducible determination of scent profiles. The effect of aging was investigated by following the response of volatile markers emitted from eight common explosives in open and closed containers over two months or two years. The initial headspace air volume consisted of a wide variety of chemical substances related to explosives, with levels varying in magnitude from low ppb to ppm. All included subsamples were affected by aging by demonstrating exponentially lower levels, and five subsamples showed a significant change in their scent profile. The dominant components decreased on a short time scale for plastic explosives based on RDX, PETN and dynamite as well as for granules of octol and ammonium nitrate mixed with fuel. For flakes of TNT, granules of Comp B and nitrocellulose powder, headspace air concentrations declined, but the overall character of their profiles were in general more stable. The overall changes, i.e., lower levels and/or changed profiles, justifies regular checks of the scent status of training materials. Considering these results together with data displaying marginal changes in energetic performance, it is advisable to complement scent training with training materials subjected to different durations of aging.     

The natural sampling of airborne trace signals from explosives concealed upon the human body.

An experimental study of the natural sampling of trace signals from explosives concealed upon the human body was performed by taking proper account of the thermal behavior of the air surrounding the human body and the particles therein. Experiments were conducted in a dispersal chamber to identify variables affecting the detectibility of concealed RDX and TNT patches. Movement by human volunteers was found to enhance the available explosive trace signal above a baseline level. Clothing blocked some of this movement-generated trace signal. The detected signal levels were also found to vary significantly from volunteer to volunteer, indicating that human variability is an issue in explosive trace detection. Further, under the conditions studied here, the detectibility of RDX and TNT was dependent upon the efficient sampling of contaminated particulate matter, not the vapor phase. The present results are now being applied to the design of a practical, nonintrusive trace detection portal for aviation security screening and related applications.     

Blood and sperm traces on human hair. A study on preservation and detection after 3-month outdoor exposure

Hair can retain important biological traces for forensic investigations. Forensic scientists are used to looking for such traces on clothing and skin of victims, however, when decomposition kicks in and all that remains of the victims is the skeleton, hair may be the only tissue representing the surface of the body at the time of a crime on which biological traces of an aggressor may have been left and still be detectable. Given the lack of research on this topic, this pilot study aims to assess the capacity of hair to retain semen and blood in hair, and the possibility to detect these fluids with well-known techniques and to obtain a useful genetic profile even when exposed to environmental conditions (Open Natural Environment (woods), Open Man Made Environment (urban)) for three months.Results showed that both traces were always visible and detectable with almost all techniques in the Control Environment, while in the two open environments some difficulties arose. However, biomolecular analysis was effective up to three months on both fluids in the Natural Environment and up to two months and one week respectively on blood and semen in the Man Made Environment. The Combur Test, OBTI, and Luminol were effective on blood up to three months in both environments while Sperm-HY-Liter and observation of cellular components were effective on semen up to at least 1 month and PSA testing was positive up to 1 week in both environments.The present work can be considered an encouraging starting point for the analysis of biological traces on hair in forensic contexts, regardless of the PMI, since blood and semen related to a crime may survive.     

Study of the adhesion of explosive residues to the finger and transfer to clothing and luggage

It is important to understand the extent of transfer of explosive particles to different surfaces in order to better evaluate potential cross-contamination by explosives in crowded security controls such as those at airports. This work investigated the transfer of nine explosive residues (ANFO, dynamite, black powder, TNT, HMTD, PETN, NH₄NO₃, KNO₃, NaClO₃) through fingerprints from one surface to another. First, the extent of adhesion of explosive residues from different surfaces to the bare finger, nitrile and latex gloves was studied. Then, the transfer of explosive residues from one surface to another through fingerprints was investigated. Cotton fabric (hereinafter referred to as cotton) as clothing material and polycarbonate plastic (hereinafter referred to as polycarbonate) as luggage material were chosen for the experiments. These surfaces containing explosive particles were imaged using a reflex camera before and after the particles were transferred. Afterwards the images were processed in MATLAB where pixels corresponding to explosive residues were quantified. Results demonstrated that transfer of explosive residues frequently occurred with certain differences among materials. Generally, the amount of explosive particles adhered to the finger decreased in the following order: skin>latex>nitrile, while the transfer of particles from the finger to another surface was the opposite. The adhesion of explosive residues from polycarbonate to the finger was found to be better compared to cotton, while the amount of particles transferred to cotton was higher.     

Detection and Identification of Explosive Particles in Fingerprints Using Attenuated Total Reflection-Fourier Transform Infrared Spectromicroscopy

Abstract:  The application of attenuated total reflection (ATR)-Fourier transform infrared (FTIR) spectromicroscopy for detection of explosive particles in fingerprints is described. The combined functions of ATR-FTIR spectromicroscopy are visual searching of particles in fingerprints and measuring the FTIR spectra of the particles. These functions make it possible to directly identify whether a suspect has handled explosives from the fingerprints alone. Particles in explosive contaminated fingerprints are either ingredients of the explosives, finger residues, or other foreign materials. These cannot normally be discriminated by their morphology alone. ATR-FTIR spectra can provide both particle morphology and composition. Fingerprints analyzed by ATR-FTIR can be used for further analysis and identification because of its non-destructive character. Fingerprints contaminated with three different types of explosives, or potential explosives, have been analyzed herein. An infrared spectral library was searched in order to identify the explosive residues. The acquired spectra are compared to those of finger residue alone, in order to differentiate such residue from explosive residue.     

Water-soaked evidence: detectability of explosive traces after immersion in water

Various factors governing the detectability of explosive traces after being soaked in water were studied. The variables are: the type of the surface (surfaces liable to be found in aircraft were chosen), the type of explosive, the type of water (tap or seawater), and movement of the immersed surface in the water. The maximal immersion times (tmax) after which explosive detection was possible were evaluated. This datum was found to depend on the type of explosive (one of the important factors is solubility in water), the surface material and the environmental conditions (tap or seawater movement). Detection of PETN on high-density polyethylene, linoleum, glass and aluminum, by the chemical Explosive Testing Kit (ETK), was possible even after a month of soaking in seawater. In addition, it has been found that movement of bulk water around the samples with deposited explosives considerably decreases tmax values. It is, therefore, recommended to retrieve samples for explosive analysis as soon as possible and in areas where the currents of water is minimal.     

A second survey of high explosives traces in public places

This survey was carried out as a follow-up to a 1994 survey carried out by this laboratory (1) in order to determine the background levels of explosives traces in public places. The first survey concentrated on transport areas and police stations in and around London. This second study examines levels in four of the United Kingdom's major cities: Birmingham, Cardiff, Glasgow, and Manchester. Samples were taken at various transport sites and from hotels, private houses, private vehicles, and clothing. The survey showed that traces of the high explosives nitroglycerine (NG), trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), and cyclotrimethylene trinitramine (RDX) are rare within the general public environment. Only one low-level trace of RDX was detected. NG, possibly associated with the use of firearms, was detected at low levels in two samples and 2,4-DNT was detected in a separate sample. No PETN was detected in any of the samples. The results of the survey indicate that it is unlikely that persons visiting public areas could become significantly contaminated with explosives. The analytical procedures employed would also have detected ethylene glycol dinitrate (EGDN) if present at levels greater than 2 ng, nitrobenzene (NB) if present at levels greater than 50 ng, mononitrotoluenes if present at levels greater than 50 ng, and the other common isomers of dinitrotoluene if these had been present at levels in excess of 10 ng. None of these were detected. The relatively high volatility of EGDN, NB, and the mononitrotoluenes would, however, cause traces of these compounds to disperse rapidly. A proportion of the samples (approximately 7%) were analyzed for the presence of HMX. No HMX was detected.