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.     

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.     

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.     

Analysis of Explosives by GC‐UV

A mixture of explosives was analyzed by gas chromatography (GC) linked to ultraviolet (UV) spectrophotometry that enabled detection in the range of 178–330 nm. The gas‐phase UV spectra of 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitrotoluene (DNT), ethylene glycol dinitrate (EGDN), glycerine trinitrate (NG, nitroglycerine), triacetone triperoxide (TATP), and pentaerythritol tetranitrate (PETN) were successfully recorded. The most interesting aspect of the current application is that it enabled simultaneous detection of both the target analyte and its decomposition products. At suitable elevated temperatures of the transfer line between the GC instrument and the UV detector, a partial decomposition was accomplished. Detection was made in real time and resulted in overlaid spectra of the mother compound and its decomposition product. Hence, the presented approach added another level to the qualitative identification of the explosives in comparison with traditional methods that relies only on the detection of the target analyte. As expected, the decomposition product of EGDN, NG, and PETN was NO, while TATP degraded to acetone. DNT and TNT did not exhibit any decomposition at the temperatures used.     

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.     

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.     

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.     

Preliminary investigation into the recovery of explosives from hair.

Sampling of hair has proved to be a useful non-invasive method for detecting illicit drugs. This study examined the viability of hair as a surface from which explosive traces can be recovered and showed that as little as one-hour vapour exposure can result in measurable traces of explosives. Contamination of the hair may result from direct contact with explosive particles or from secondary contact by hand. Also the paper demonstrates that hair can concentrate explosive from the ambient vapour of a variety of military explosives. It was found that the amount of TNT picked up by the hair increased with time of vapour exposure. The data also suggested that unwashed hair may pick up more TNT than washed hair.     

Particle characteristics of trace high explosives: RDX and PETN

The sizes of explosives particles in fingerprint residues produced from C-4 and Semtex-1A were investigated with respect to a fragmentation model. Particles produced by crushing crystals of RDX and PETN were sized by using scanning electron microscopy, combined with image analysis, and polarized light microscopy was used for imaging and identifying explosive particles in fingerprint residues. Crystals of RDX and PETN fragment in a manner that concentrates mass in the largest particles of the population, which is common for a fragmentation process. Based on the fingerprints studied, the particle size to target for improving mass detection in fingerprint residues by ion mobility spectrometry (IMS) is > or = 10 microm in diameter. Although particles smaller than 10 microm in diameter have a higher frequency, they constitute < 20% of the total mass. Efforts to improve collection efficiency of explosives particles for detection by IMS, or other techniques, must take into consideration that the mass may be concentrated in a relatively few particles that may not be homogeneously distributed over the fingerprint area. These results are based on plastic-bonded explosives such as C-4 that contain relatively large crystals of explosive, where fragmentation is the main process leading to the presence of particles in the fingerprint residues.     

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.     

Evaluation of different sampling media for their potential use as a combined swab for the collection of both organic and inorganic explosive residues

Commercially available skin cleansing alcohol wipes and conventional swabs were investigated for their use as a universal sampling medium for the simultaneous collection of both organic and inorganic explosive residues. Six compounds with the potential to be encountered in casework [pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), triacetone triperoxide (TATP), ammonium nitrate, and sodium chlorate] were selected as representative target compounds. Quantities of these target compounds were deposited on four different substrates (glass, plastic, aluminium foil and laminate). Two chosen alcohol wipes demonstrated better overall performance in the recovery of both the organic and inorganic representative compounds from each of the test surfaces compared to the results obtained using conventional cotton and polyester swabs, pre-moistened with various solvents, and a direct methanol wash (used as a control). Results obtained using dry cotton swabs indicated that it was not an effective swabbing system for the collection of both organic and inorganic explosive residues on common substrates.     

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS) — Preliminary study on TATP and PETN

The application of isotopic techniques to investigations requiring the provision of evidence to a Court is limited. The objective of this research was to investigate the application of light stable isotopes and isotope ratio mass spectrometry (IRMS) to solve complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques.Due to the current threat of organic peroxide explosives, such as triacetone triperoxide (TATP), research was undertaken to determine the potential of IRMS to differentiate samples of TATP that had been manufactured utilising different starting materials and/or manufacturing processes. In addition, due to the prevalence of pentaerythritoltetranitrate (PETN) in detonators, detonating cord, and boosters, the potential of the IRMS technique to differentiate PETN samples from different sources was also investigated.Carbon isotope values were measured in fourteen TATP samples, with three definite groups appearing in the initial sample set based on the carbon data alone. Four additional TATP samples (in a second set of samples) were distinguishable utilising the carbon and hydrogen isotopic compositions individually, and also in combination with the oxygen isotope values. The 3D plot of the carbon, oxygen and hydrogen data demonstrated the clear discrimination of the four samples of TATP. The carbon and nitrogen isotope values measured from fifteen PETN samples, allowed samples from different sources to be readily discriminated.This paper demonstrates the successful application of IRMS to the analysis of explosives of forensic interest to assist in discriminating samples from different sources. This research represents a preliminary evaluation of the IRMS technique for the measurement of stable isotope values in TATP and PETN samples, and supports the dedication of resources for a full evaluation of this application in order to achieve Court reportable IRMS results.     

Optimizing Accu Time‐of‐Flight/Direct Analysis in Real Time for Explosive Residue Analysis

The use of a direct analysis in real time (DART) mass spectrometer (MS) instrument was optimized for 22 compounds of organic explosive residues to provide a guide for DART‐MS users in rapid screening of explosive compounds. Samples were introduced as neat solutions and sequential dilutions to determine optimal instrument conditions and lowest concentration detectable. Most compounds were optimized to 250°C in the negative ion mode, and several compounds benefited from the addition of a chloride dopant from methylene chloride (amino‐dinitrotoluenes, RDX, EGDN, and PETN). Few compounds were more sensitive in the positive ion mode (TEGDN, DEGDN, HNS, and DMNB). Mixtures of compounds were detected using clean room wipes, directly from their surfaces and from subsequent extractions. Compounds from the mixtures were also successfully detected in soil and from swipes of spiked surfaces. The instrument showed merit in detection of pg/μL solutions for most of the compounds and among the substrates tested.     

有机爆炸物的现场非介入性检测——顶空固相微萃取一真空气相色谱质谱法

本文考察了顶空固相微萃取在有机爆炸物现场非介入性检测中的适用性。由固相萃取（SPME）纤维头吸附的有机爆炸物用真空气相色谱一质谱联用仪进行检测。该方法所需的洗脱温度低,色谱分离时间短。SPME适用于提取蒸汽压不低于2．4,6-三硝基甲苯（TNT）的挥发性和半挥发性有机爆炸物,如较易挥发且不稳定的化合物三过氧化三丙酮（TATP）的非介入性检测就可以应用该方法。本研究使用静态顶空,尽可能地减少顶空体积,实现了较高的灵敏度。在现场,SPME方法的灵敏度受环境温度的影响较大：由于样品的蒸汽压未达到平衡,在固定顶空体积和萃取时间的条件下,SPME纤维头萃取的样品总量随温度的提高而增加。在有合适容器的情况下SPME纤维头上萃取的样品在取样3天后仍然能顺利检测。     

Destruction of Peroxide Explosives

Abstract:  Chemicals containing multiple peroxide functionalities, such as triacetone triperoxide (TATP), diacetone diperoxide (DADP), or hexamethylene triperoxide diamine (HMTD), can be explosive. They are impractical and are not used by legitimate military groups because they are shock and heat sensitive compared to military explosives. They are attractive to terrorists because synthesis is straightforward, requiring only a few easily obtained ingredients. Physical removal of these synthesis products is highly hazardous. This paper discusses methods to degrade peroxide explosives chemically, at room temperature. A number of mixtures containing metals (e.g., zinc, copper) and metal salts (e.g., zinc sulfate, copper chloride) were found effective, some capable of destroying TATP solutions in a few hours. Strong acids proved useful against solid peroxide materials; however, on a 1 g scale, addition of concentrated sulfuric acid caused TATP to detonate. Thus, this technique should only be used to destroy small-laboratory quantities.     

X射线衍射法检验有机炸药初探

目的 建立X射线衍射法（XRD）检验有机炸药的方法.方法 使用X射线衍射仪对有机炸药苦味酸（PA）,太安（PTEN）,黑索金（RDX）,梯恩梯（TNT）进行测试分析.结果 准确测定出有机炸药的物质组成及结构.结论 该方法能够直接给出有机炸药的分子式及结构组成,定性准确,操作简便,可用于有机炸药的定性检测.     

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.     

Characterization of an odor permeable membrane device for the storage of explosives and use as canine training aids

The storage and use of explosives is regulated at the state and federal level, with a particular focus on physical security and rigorous accounting of the explosive inventory. For those working with explosives for the training and testing of explosive-detecting canines, cross-contamination is an important concern. Hence, explosives intended for use with canine teams must be placed into secondary storage containers that are new, clean, and airtight. A variety of containers meet these requirements and include screw-top glass jars (e.g., mason jars). However, an additional need from the explosive-detecting canine community is secondary containers that can also be used as training aids whereby the volatiles emitted by explosives are emitted in a predictable and stable manner. Currently, a generally accepted method for the storage of explosives and controlled emission of explosive vapor for canine detection does not exist. Ideally, such containers should allow odor to escape from the training aid but block external contaminates such as particulates or other volatiles. One method in use places the explosive inside a permeable cotton bag when in use for training and then stores the cotton bag inside an impermeable nylon bag for long-term storage. This paper describes the testing of an odor permeable membrane device (OPMD) as a new way to store and deploy training aids. We measured the evaporation rate and flux of various liquid explosives and volatile compounds that have been identified in the headspace of actual explosives. OPMDs were used in addition to traditional storage containers to monitor the contamination and degradation of 14 explosives used as canine training aids. Explosives were stored individually using traditional storage bags or inside an OPMD at two locations, one of which actively used the training aids. Samples from each storage type at both locations were collected at 0, 3, 6, and 9 months and analyzed using Fourier Transform Infrared (FTIR) Spectroscopy and Gas Chromatography–Mass Spectrometry (GC–MS) with Solid-Phase Microextraction (SPME). FTIR analyses showed no signs of degradation. GC–MS identified cross-contamination from ethylene glycol dinitrate (EGDN) and/or 2,3-dimethyl-2,3-dinitrobutane (DMNB) across almost all samples regardless of storage condition. The contamination was found to be higher among training aids that were stored in traditional ways and that were in active use by canine teams.     

Sourcing explosives: A multi-isotope approach

Although explosives are easily identified with current instrumental techniques, it is generally impossible to distinguish between sources of the same substance. To alleviate this difficulty, we present a multi-stable isotope (δ¹³C, δ¹⁵N, δ¹⁸O, δD) approach for appraising the possibility of discriminating explosives. The results from 30 distinct PETN, TNT and ANFO samples show that the different families of explosives are clearly differentiated by both their specific isotope signatures and their combination with corresponding element concentrations. Coupling two or more of the studied isotope systematics yields an even more precise differentiation on the basis of their raw-material origin and/or manufacturing process.