Counterterrorist Detection Techniques of Explosives

Israel

Chapter 1

Detection of Explosives by Chemiluminescence

Ana M. Jimenez,

Maria J. Navas,     Department of Analytical Chemistry, Faculty of Pharmacy, University of Seville, 41012 Seville, Spain

Publisher Summary

This chapter aims to understand the various advantages of trace detection systems based on Chemiluminiscence (CL) for the detection of explosives containing nitrogen. The literature discusses 25 years’ research and advancement in the field of CL and its use for the detection of explosives. The earliest papers of the 70s and 80s have been used because they comprehensively discuss how the various techniques work. The basic aim is to provide an understanding of the potential and implementation of CL systems for detecting trace explosives. The first section of the chapter is an introduction that describes the concept and principles of CL and how it can be utilized in the field of explosives. The second section describes the application of CL in the field of explosives with focus on thermal energy analyzer (TEA), because it has an important role to play in trace detection of explosives. It also describes the applications of Luminol CL and Electrochemiluminescence (ECL) for the detection of explosives. The final section describes how CL can be used to detect explosives for security measures. This is because much of this research is directed toward the safety of civilians.

Contents

1. Introduction

2. Chemiluminescence systems in explosive analysis

3. Using chemiluminescence as detection technology in security

References

1 Introduction

The aim of this chapter is to explore the real and potential advantages of chemiluminescence (CL)-based trace detection systems for the detection of a broad group of explosives containing nitrogen. The literature reviewed covers about 25 years of research and advances in the use of CL for detecting explosives, from the 1980s to May 2006. Because the earliest papers in the 1970s and 1980s comprehensively describe how these techniques operate, we have used them to provide concepts and general information. The literature has been summarized to provide a contemporary understanding not only of the potential of CL systems but also of their implementation in many laboratories for the detection of trace explosives.

The chapter has been structured into several sections: first, there is a brief introduction, including a description of the concept and general principles of CL and how it is used in the field of explosives. The second section describes CL applications in the field of explosives and focuses in particular on the thermal energy analyser (TEA) because of its important role in the trace detection of explosives. The recent applications of luminol CL and electrochemiluminescence (ECL) to explosive detection are also described. Finally, because much of the research into explosive detectors has been directed towards civilian safety, a third section describes how CL is used as a security measure to detect explosives.

1.1 Principles of chemiluminescence

Energy can be transferred into (and out of) matter in many different ways, as heat and light or by chemical reactions. When energy is released by matter in the form of light, it is referred to as luminescence. An exception is usually made for matter that has such a high temperature that it simply glows; this is called incandescence. When energy in the form of light is released from matter because of a chemical reaction, the process is called CL [1]. CL is the generation of electromagnetic radiation (ultraviolet, visible or infrared) as light by the production of an electronically excited species from a number of reactants which goes on to release light in order to revert to its ground state energy. While the light can, in principle, be emitted in the ultraviolet, visible or infrared region, reactions emitting visible light are the most common. They are also the most interesting and useful. When the chemiluminogenic reaction occurs within living organisms, the phenomenon is named bioluminescence. CL in analytical chemistry has numerous advantages, such as superior sensitivity, safety, rapid and simple assay and controllable emission rate. However, it also has such disadvantages as poor reproducibility and long observation times. The CL process takes place at the rate of a chemical reaction, and the factors that affect emission intensity are in fact a combination of chemical reaction rate and luminescence considerations. A CL reagent may yield significant emission not just for one unique analyte, CL emission intensities are sensitive to a variety of environmental factors such as temperature, solvent, ionic strength, pH and other species present in the system, and the emission intensity from a CL reaction varies with time [2]. Today, many chemiluminescent systems are known, both biological and non-biological. Numerous inorganic and organic chemical reactions produce light because one of the reaction products is formed in an electronically excited state and emits the radiation on falling to the ground state.

A general description of the reactions is as follows:

where ‘*’ indicates an electronically excited state [3]. This would be a rather simple case and would be classified as direct CL. In many systems, the initially excited state molecule is used as a conduit of energy to excite a second or third molecule that is the actual emitting species. When energy is transferred to an effective fluorophore (F) added to the system, the luminescence intensity increases considerably.

This would be classified as indirect, sensitized or energy transfer CL.

Nowadays, CL methods are a real alternative in analytical fields, and the applications that determine a wide variety of compounds have been extensively discussed in the literature.

1.2 Using CL to reveal the presence of explosives

Explosive detection techniques can be broadly classified into two main categories: bulk detection and trace detection. CL is commonly regarded as a trace detection technology. Trace detection involves the chemical detection of explosives by collecting and analysing tiny amounts of explosive vapour or particles (a microscopic amount of explosives) [4] and looking for residue or contamination from handling or being in proximity to explosive materials. Microscopic particles of solid explosive materials can adhere to a wide variety of surfaces (Teflon, glass, metal, plastic, etc.), and they can be detected by wiping the surface. Vapour detectors examine the vapour emanating from a liquid or a solid explosive, and because some explosives have a low vapour pressure, these detection techniques would be very sensitive.

Nitrogen-explosive compounds usually analysed by CL may be classified under three structural categories: (i) nitroaromatic compounds, (ii) nitrate esters and (iii) nitramines. Examples of nitro-substituted hydrocarbons are nitromethane, trinitrobenzene (TNB), trinitrotoluene (TNT) and pentantiroaniline. Nitroglycerine (NG), ethylene glycol dinitrate (EGDN) and pentaerythritol tetranitrate (PETN) are nitrate esters [5]. The nitro-explosive compounds that are the result of the presence of nitro and nitrate groups can be detected by CL methods, as we shall describe below (Section 2). A list of the most widely used nitrogen-containing explosives commonly determined by CL is given in Table 1. As explosives are usually referred to with an abbreviation, the Table gives both the compound name and the abbreviation. Figure 1 gives the structures of nitroaromatic and nitramine explosives commonly determined by CL.

Table 1

List of common nitrogen-containing explosives analysed by chemiluminescence

Fig. 1 Structures of nitroaromatic and nitramine explosives commonly determined by chemiluminescence. DNT, dinitrotoluene; HMX, cyclotertamethylene tetranitramine; NT, nitrotoluene; RDX, cyclotrimethylene trinitramine; TNT, trinitrotoluene.

Reviews and other papers (e.g. official reports or guides about instrumentation designed for explosive detection) describe CL as a reliable trace detection system for nitro explosives [4,6–13]. In a recent review, Moore [12] pointed out that vapour or particle detection systems are best suited for personnel monitoring. He has also stated how difficult it is to detect explosives, among other reasons, because of the low vapour pressure of most common explosives, vanishingly small in the case of the highest priority explosives, the attenuation of vapour by packaging or the thermal degradation of the material when the temperature is raised to achieve higher vapour pressure. Therefore, methods that relay on sampling of air spaces need to either sample very large volumes or have exceedingly small detection limits. Fine et al. [14] have pointed out that an ideal technique for ultra-trace analysis of explosives would be both simple and rapid, require minimal sample clean-up, be sensitive to as little as 1–10 pg quantities of all the compounds of interest and would work equally well both on complex samples from the real world and on high-grade laboratory standards made up in pure solvents. CL systems have many of the aforementioned qualities, and so it is one of the more commonly used techniques for detecting explosives [7].

Nevertheless, the use of CL for detecting explosives does have some drawbacks although some of them can be overlooked. First, it is limited to nitrogen-containing explosives. This does not reduce its usefulness too much because most major explosives are nitrogen compounds although it clearly makes it impossible to use CL to detect some types of explosives, such as peroxide explosives, that have become particularly important in forensic investigations because of the emergence of terrorist threats and crimes in which these explosives have been used [15]. The second disadvantage has to do with selectivity: CL per se is not capable of identifying what type of explosive molecule is present because several compounds, including those commonly used as taggants in plastic explosives, also contain NO2 groups. This lack of selectivity inherent to most CL methods can be overcome by coupling CL with separation techniques. CL explosive detection technologies are usually fitted with a front-end gas chromatograph column. High-performance liquid chromatography (HPLC) or supercritical fluid chromatography (SFC) has been less used. The use of separation methods is also recommended because explosive residues usually have to be determined in complex matrices.

CL technology is a real alternative in trace explosive detection. It has excellent sensitivity and selectivity when combined with high-speed gas chromatography (GC). A wide range of explosives is detectable, including EGDN, NG, ammonium nitrate fuel oil (ANFO), TNT, dinitrotoluene (DNT), cyclotrimethylene trinitramine (RDX) and PETN. The detector does not require a radioactive source, and this can reduce both time and paperwork when transporting the system [16]. Commercial systems, easily hand-held or portable, are available and being used as security systems in different kinds of installations, such as in airports or forensic laboratories. A considerable number of papers have reported the application of luminol CL, anyway ECL and immunoassay (IM) techniques for explosive detection. Nevertheless, most of these papers deal with the CL reaction of the nitrosyl (NO) radical with ozone and the use of the TEA manufactured by Thermo Electron Corporation (Waltham, MA, USA). Section 2 deals with NO–ozone CL (TEA), luminol CL and ECL detection systems in their applications to the trace detection of explosives and briefly summarizes the reactions and mechanisms involved.

2 Chemiluminescence systems in explosive analysis

2.1 Thermal energy analyser

Thermal energy analyser is a gas-phase CL detector that responds specifically to nitrogen compounds. Most common explosive materials contain nitrogen in the form of either nitro or nitrate groups that pyrolyse to produce NO or NOx, which is the main reason why CL can be applied. TEA was developed by Fine and coworkers [17,18], and at first, it was mainly used for the detection of N -nitrosamines in complex matrices or analytes of medical interest, such as vasodilators and their metabolites in human blood [19]. In these fields, the development of the CL-specific nitrogen detector during the 1970s was a major advance. Although the TEA detector can be used with both gas and HPLC in explosive detection, most applications couple TEA to GC, and the earliest references to it being used with explosives that appeared during the 1980s [20–24]. TEA is described [23] as a very useful chromatographic detector for the forensic trace analysis of explosives. Its high sensitivity and selectivity for nitro compounds allow the rapid screening of contaminated extracts for traces of explosives, the majority of which contain nitro groups, with the minimum likelihood of false-positive results. A detailed description of the detector and the physical principles of its operation can be found in the literature [25–27].

2.1.1 Analytical considerations

2.1.1.1 The chemiluminescence reaction

The fundamental operating principle of TEA is based on the CL reaction between nitric oxide and ozone, which can be schematized as follows [28]:

The nitric oxide reacts with ozone to produce an electronically excited specie (NO2*) that decays back to its ground state emitting light in the infrared spectral region (600–2800 nm).

2.1.1.2 Mode of operation

The earliest references above mentioned (Subsection 2.1) describe the fundamental operating principle of the TEA, which can be briefly summarized as follows: the components of interest eluting from the chromatograph are introduced into a catalytic pyrolyser where NO2 is released from organic nitro compounds and simultaneously converted into a NO radical by the catalytic surface. The gaseous pyrolysis products are swept by a carrier gas from the pyrolyser through a cold trap (–100 or – 150°C) or a solid sorbent device where most contaminants are condensed, but NO radicals survive. The ozone reaction generally takes place at reduced pressure in a reaction chamber where the NO radical is oxidized by ozone to form the electronically excited species NO2* that is detected by an appropriate photomultiplier tube (PMT). This operating principle produces peaks only for substances containing nitro or nitroso groups. Because the intensity of light from the chemiluminescent reaction can be increased at reduced pressure, a vacuum pump is always used. A red cut-off filter is used to eliminate light emission resulting from potential interferences. A schematic diagram of the TEA is shown in Fig. 2.

Fig. 2 Simplified schematic of the thermal energy analyser. Reprinted from Fine et al. [ 25]. Copyright (1975), with permission from Elsevier.

One nice feature of CL detectors is that they do not use a radioactive ionization source [29] and thus avoid some of the paperwork and regulatory oversight that may be associated with ion mobility spectrometer detectors.

2.1.1.3 Sampling and preparation of the samples

The papers reviewed show that the general procedure for collecting organic explosive residues from surfaces includes cotton swabs or vacuum onto a filter. Owing to the complexity of the samples (debris from the scene of an explosion, contaminated soil, etc.) and/or the need for pre-concentration, samples often require pre-treatment, which eliminates possible interfering substances. So the literature reviewed also contains reports on such sampling methodologies as solid-phase extraction (SPE) or supercritical fluid extraction (SFE), which describe how they are used to isolate explosives in combination with chromatographic techniques.

A common procedure for taking samples consists of using solvent-moistened cotton wool swabs. The same solvents are then often used to extract the explosive residues from the soaked cotton swab. Acetone is one of the most commonly used solvents because explosive compounds dissolve easily in it; however, the drawback is that it also dissolves other non-desirable compounds.

Douse used a dynamic headspace method to improve the clean-up of gunshot residues before detecting NG by capillary column GC–TEA [30]. Handswabs and vacuumed clothing samples were generated and placed in a luer lock glass syringe fitted. Syringes containing filters with residues were then inserted in a headspace apparatus. A column containing Amberlite XAD-7 beads was eluted in the following sequence: (i) pentane to elute nitrobenzene (NB) and 4-nitrotoluene (4-NT); (ii) pentane-methyl-tert-butyl ether (pentane-MTBE) to elute unwanted coextractives and (iii) ethyl acetate to elute NG and other explosives. The syringe containing residual material was clamped vertically, and MBTE was passed through it. The solution was passed through a glass column containing XAD-7 beads. Explosives were eluted with ethyl acetate, and this fraction was evaporated under a stream of nitrogen. NG and other explosives were detected by GC–TEA.

Thompson et al. [31] compared the aqueous recovery and acetone extraction from cotton swabs of organic explosive residue, which was generated by mixing standards in motor oil on aluminium foil, by detonating four different bombs hidden inside suitcases filled with clothing and by handling plastic explosives. The explosives were isolated by SPE, using a poly-N -vinylpyrrolidone-divinyl-benzene sorbent. Samples were screened by liquid chromatography-ultraviolet (LC-UV), and the presence of explosives was confirmed by LC– or GC–mass spectrometry (MS) and fast GC–TEA (EGIS). The authors concluded that the water extraction/SPE procedure was an effective process for treating organic explosive residue on cotton swabs for subsequent analysis by LC.

Kolla [32] used SPE and GC–TEA to prepare and analyse samples of explosives and found that SPE was the most useful way of reducing the contamination of the column by accompanying substances. The SPE columns were 500-mg RP18 (3 cm) columns. The original sample, whether dust or swabs, was extracted with acetone in a Soxhlet extractor. The acetone was then evaporated and the sample dissolved in acetone and diluted at 1:10 with water. After washing, the elution was performed with three volumes of methanol. After the methanol had been evaporated, the sample was dissolved in a small volume of acetone for GC–TEA.

The effectiveness of using SFE coupled to GC with a thermal desorption modulator (TDM) interface and TEA detection to analyse explosives has been evaluated by Francis et al. [33] in soil samples and standards.

2.1.1.4 Pyrolyser

In the analysis of nitroaromatic explosives, TEA is similar to the systems used for nitrosamines except for the fact that temperatures must be higher. Several papers have reported that the temperature of the TEA pyrolysis furnace can affect the selectivity of the detector. A study carried out by Douse [34] to detect traces of several explosives at the low nanogram level revealed that the chromatograms obtained by GC–TEA for both pure compounds and spiked handswabs clearly showed the superior selectivity of TEA in reducing the temperature from 800 to 700°C. Reduction from 700 to 550°C further demonstrated the selectivity of TEA, but this was offset by a partial loss of response for all explosives. It was found, however, that the selectivity of TEA using a pyrolysis of 550°C was such that as much as 13% of the sample could be analysed with little effect on the background. On the contrary, from the literature reviewed, it can be seen that, for nitroaromatic compounds, the release of nitric oxide was maximum between 800 and 950°C (though even 1000°C has been reported) [21]. Lafleur and Mills [20] studied the pyrolytic release of nitric oxide (produced from a series of NTs) as a function of temperature. The response was maximum at temperatures above 800°C and decreased by almost three orders of magnitude at temperatures below 500°C. They finally selected a temperature of 900 °C to ensure maximum thermal decomposition and thus maximum release of nitric oxide. The relative response was highly reproducible, and the release of nitric oxide was, therefore, also reproducible but not necessarily molar; that is, one nitro group did not necessarily yield one molecule of nitric oxide. Relative molar response ranged from 0.59 (2-NT) to 2.25 (2,4,6-TNT). A pyrolysis temperature of 950°C was chosen by Phillips et al. [35] to determine nitroaromatics, NB, 2,4-DNT and 2,6-DNT in biosludges by GC/TEA.

Selavka et al. [36] have reported that for LC, a pyrolysis chamber temperature greater than 550°C gives rise to substantial baseline noise, which severely limits the detector’s sensitivity and selectivity. Thus, LC–TEA is always performed in the ‘nitroso mode’ (the pyrolyser is held at 550°C).

2.1.1.5 Selectivity

The use of a selective detection system is of primordial importance in reducing or eliminating interference in the signal of the analytes of interest. In this respect, TEA coupled to chromatographic techniques is one of the most selective devices. When TEA is used, the analytical signal is not affected by compounds without nitro functional groups, which may be in the sample. Fine et al. [14,26] have suggested that four factors are responsible for TEA’s high degree of selectivity. First, only compounds that have NO2 or NO functional groups can give a response. Second, the reactive species must survive the –100°C cold trap. For highly contaminated samples, this temperature can even be – 160°C. At these temperatures, the vapour pressure of the NO radical is greater than 1 atm, whereas the vapour pressure of almost all organic compounds is substantially less. Third, the reactive species must react with ozone to produce a chemiluminescent light in a narrow range between 600 and 800 nm. Fourth, the reaction with ozone must be sufficiently rapid to take place during the residence time of the species in the reaction chamber. Phillips et al. [35] have compared the TEA results with those of other selective GC detectors (thermionic specific, electron capture and Hall electrolytic conductivity) to analyse nitroaromatics in biosludges. The chromatograms obtained from spiked extracts with the other detectors all contained many interfering compounds that eluted at retention times close to the nitroaromatics, which made it necessary to modify the sample workup so that the samples were amenable to the different selective detectors. They found that the selectivity of the TEA made sample clean-up unnecessary and solved all the problems of the solvent effects.

The Guide for the Identification of Intact Explosives from The Technical Working Group on Fire and Explosion (TWGFEX) of the National Center of Forensic Science [37] classified the analytical techniques into four categories, and GC–TEA and LC–TEA were in the category that provides a high degree of selectivity.

2.1.1.6 Sensitivity

Traces of explosives are commonly present in very low levels in samples that are analysed, so it is important to take sensitivity into account when designing detectors for explosive detection. As a rough ‘rule of thumb’, Nambayah and Quickenden [38] reported that a method suitable for direct explosive vapour detection should be able to detect explosive concentrations at less than 1 ng/L. They made an exhaustive study of the lowest experimental detection limits achieved with various analytical techniques reported in the literature on traces of explosive, and they informed that headspace GC-electron capture detector (ECD) followed by immunosensor techniques achieves the lowest detection limits (from 0.07 to 20 ng/L).

The literature reviewed shows that GC/TEA methods can be extremely sensitive and respond to a few picograms of common explosives. Fine et al. [14] using GC/TEA (capillary columns) found that the minimum detectable level at a signal-to-noise ratio of 3:1 is estimated to be 4 pg for TNT and RDX; 5 pg for EGDN, NG and DNT; and 25 pg for tetryl when they determined explosives in ‘real world’ samples without previous clean-up.

Although the reported sensitivity of TEA when it is used in combination with HPLC or packed column GC to analyse explosives is only in the low nanogram range, Douse [21] described a method that uses fused silica capillary column GC in conjunction with TEA detection for trace analysis of explosives in the low picogram range. He reported that silica capillary column GC can be used to overcome the problems of very polar explosives adsorbing on the packed columns used for GC analysis and in the transfer lines of the TEA. In this way, the detection limits were lowered. He also concluded that the minimum detectable levels (15,10 and <200 pg for NG, TNT and RDX, respectively) of the compounds studied were similar to those obtained when ECD was used.

2.1.2 Applications of TEA to the analysis of explosives

For complex matrices, a separation technique used to be necessary to obtain a clean sample for explosive analysis. Also, because of the lack of selectivity of CL, explosives are generally introduced into the TEA after separation. Chromatographic techniques coupled to sensitive detection systems are widely used to detect explosives. Most of the TEA methods for detecting and identifying nitrogen-containing explosives rely on GC separation techniques, as can be seen in most of the literature reviewed and in the commercial technologies available today. TEA in combination with certain chromatographic techniques can exhibit detection limits in the low picogram range. Its selectivity is good, and it has become the method used for detection and confirmation by a considerable number of laboratories. As far as we know, there has been little bibliography on HPLC and SFC, but some earlier papers suggest that they may be able to be used for explosive analysis. The selective and sensitive detection of explosive compounds by coupling HPLC with TEA has been limited to nitrate esters and nitramines, because when nitroaromatic compounds have been investigated under the same conditions, the molar response is relatively poor [20,39].

2.1.2.1 Gas Chromatography–thermal energy analyser

In GC, a sample containing the compounds of interest, which may be gas or liquid, is pushed through a column by an inert carrier gas (the mobile phase). The sample moves through a packed or capillary column at different speeds. The sample’s components are separated and emerge at different ‘retention times’ because they are distributed differently between the mobile and the stationary phases. The detection system responds to the presence and concentration of the separated compounds, thus making it possible to identify and quantify them.

The potential of GC, HPLC and ion chromatography (IC) coupled with sensitive detection techniques, including TEA, for the trace detection of explosives has been investigated by Kolla [40]. GC is preferred for organic compounds, which can be vapourized without decomposition. Most of the explosives that can be detected by TEA belong to this group. TEA with GC is presented as one way of solving some of the problems associated with MS (i.e. the identification of nitrate esters or RDX in complex matrices). Kolla has pointed out that GC is the method of choice in general analytical operations, but the usual GC systems have to be applied with slight modifications because not every explosive is stable at higher temperatures. In order to be able to analyse all explosives, a compromise has to be found for GC conditions. An injection port with an insert that traps the non-vapourizable substances should be used (a split-splitless injector with a fritted glass insert). The optimum injection temperature was 170°C. The column used was a 10-m DB-5 capillary column. The column temperature was initially 50°C and was increased gradually to 250°C (10°C/min). A polymethylphenyl (5%) siloxane (DB-5) was used to enhance the selectivity of the column for the nitro compounds. Despite the specificity for nitro and nitroso compounds, in some samples, in addition to the explosive constituents, many unidentified peaks appeared in the chromatogram. The author pointed out the need for confirmation with at least one different method that must have a similar sensitivity and should have also a selective detector. A simple column change to a stationary phase of different polarity (that is to say, a stationary phase with a higher phenyl content or with additional cyanopropyl groups in polymethylsiloxane) in the GC–TEA system may make this confirmation possible. The author also reported that the TEA detector can be coupled to HPLC, but the greatest disadvantage of this approach is the lower sensitivity that results from broad peak shape and poor resolution. Confirmation is also possible by GC–MS or electron capture detector. The first, though well suited to the determination of nitroaromatics, presents some of the problems already mentioned, and the second, because of its lower selectivity, is only recommended if the matrix is relatively clean. Another paper published by Kolla and Sprunkel [41] deals with the identification of dynamite explosives in post-explosion residues. In the post-blast residues of dynamites that contain nitroaromatic compounds (i.e. European dynamites), the isomers of DNT and/or TNT can be detected, so it is possible to identify dynamite by determining the ratios of the nitroaromatic constituents. Six German dynamites were selected, and their compositions were analysed. The dynamites selected were detonated as free hanging charges, and the samples, taken from metal plates placed at different distances from the centre of the explosion, were analysed by GC–TEA.

The effectiveness of coupling SFE/GC with TDM and TEA detection was evaluated by Francis et al. [33] as a system for analysing explosive compounds [1-nitropyrene (1-NP), 2-nitronaphthalene (2-NN), 2,4-DNT, 2,6-DNT, 1,3,5-TNB, TNT, PETN, RDX and NG] in soil samples and standards. The system can be used for screening small samples in short periods of time. Citing other investigators, the authors claim that the system has the following advantages: it allows the extraction process to be monitored in real time, it provides very small injection bands for sample introduction and it is compatible with narrow-bore capillary columns. This study used neat or modified carbon dioxide (CO2) as mobile phase and capillary columns (50 mm ID) with methylpolysiloxane and p, p ‘-cyanobiphenylmethylpolysiloxane stationary phases. Nitroaromatic compounds were easily extracted and eluted, but nitrate esters (PETN and NG) decomposed during thermal desorption in the modulator (a direct correlation between the temperature of the TDM and the extent of the decomposition was observed), which is one of the limitations of the method. Organic modifiers (15% acetone) had to be used to improve the extraction of some explosives, such as TNB or 1-NP. Nitramine or RDX could not be extracted under these conditions, and the use of methanol as a modifier for their extraction led to plugging of the 5-mm ID restrictor. The analysis of 200 mg of soil samples containing 24 ppb of 2,4-DNT (data obtained by GC/MS and SFC/MS) was complete in less than 10 min, and the minimum detectable quantity for 2,4-DNT was found to be 2.6 ppb (S/N = 3). The authors concluded that the proposed method can quickly analyse relatively volatile and thermally stable nitro compounds from solid matrices.

Trace explosive detection is a typical activity of forensic laboratories, and several laboratories involved with explosive investigations have adopted GG–TEA for this purpose. In several publications, Douse (from The Metropolitan Police Forensic Science Laboratory, London, UK) has described the application of capillary column GC–TEA to the trace analysis of explosives. Some of his preliminary papers [21,34] have shown that this combination leads to very broad peaks that impair resolution and thus reduce the power of the method for identifying and discriminating peaks due to unknown explosives. Attempts at improving the peak shape by optimizing the chromatographic conditions were unsuccessful. So, subsequent studies describe modifications in the TEA detector to improve selectivity [22]. Samples were cleaned up using columns of Amberlite XAD-7 beads and mixture of methyl tert-butyl ether and n -pentane as eluting solvent when necessary. TEA operating conditions included TEA pyrolysis oven temperature between 550 and 800°C, an ozone flow rate of 1.3 mL/min and a reaction chamber pressure of 0.29 mm Hg at an oven temperature of 60°C. One modification consisted of replacing the standard amplifier by a different amplifier and noise filtration system that gave better peak shape. Under the optimum conditions, 5 pg of NG, TNT and RDX were readily detectable. Moreover, selectivity was better when the pyrolyser catalyst tube normally fitted on the TEA detector was replaced with a length of silica capillary tubing. The selectivity of the system was such that vacuum extracts from clothing could be analysed for traces of organic firearms discharge residue without the need for sample clean-up. In addition, the cryogenic trap could be eliminated when TEA was used for trace analysis in contaminated extracts. Another advantage of the silica pyrolysis tubes reported by the author was the low price of replacement lengths of uncoated capillary, their long lifetime and the extreme ease of replacement of the pyrolysis column. As Douse has reported, these modifications considerably simplify routine operation and the maintenance of the TEA detector. Collins continued these studies [24] and in a subsequent paper identified the source of the peak broadening within the electronic circuitry. He also described a simple modification of the TEA [the original capacitor C2 (0.47 μF) was first replaced with a 0.1-μF component and later with a 0.022-μF capacitor], which results in much better capillary GC peak shape. Nevertheless, the above modifications resulted in more noise, which was obtrusive at higher sensitivities. To minimize this last problem, the author described the use of a supplementary electronic filter.

Subsequently, Douse [30] used the GC/TEA system to detect NG in gunshot residues. With pure standards, it was possible to detect down to about 5 pg of NG, but such sensitivity cannot be achieved with extracts from handswabs or vacuumed samples from clothing, for such extracts were substantially contaminated with lipids and other materials. The clean-up is adequate for many samples, but during experiments on clothing, it was frequently found that contamination was too great. This was studied, and a procedure was developed that exploits the volatility of NG to provide a primary clean-up by trapping the NG vapour on to XAD-7 beads, followed by solvent elution and GC–TEA detection. The dynamic headspace procedure described effectively separates volatile explosives such as NG from involatile impurities that reduce the selectivity. By trapping the volatilized explosives on to XAD-7 beads and effecting additional clean-up, detection limits of sub-nanogram quantities per swab or filter can be achieved. The results confirmed that the GC/TEA system is a robust combination that provides both sensitivity and selectivity.

Since 1989, GC–TEA has been used by the Forensic Explosive Laboratory (FEL; Kent, UK) as one of the techniques for explosive trace analysis. In this year, the FEL established a weekly quality assurance testing regime in its explosive trace analysis laboratory in an attempt to prevent the accumulation of explosives, which could result in contamination of samples and controls. GC–TEA was usually used for initial sample screening and identification. Confirmation was carried out when possible by GC–MS. The GC–TEA systems adopted were essentially as described in a previous paper by Douse [34]. Since 1989, several articles have described the results obtained by the FEL investigators during approximately a decade. The general procedures and conditions for organic explosives are summarized below. They use cotton wool swabs or vacuum onto a filter for sampling (with two different sampling solvents: a mixture of ethanol and water in equal volumes and methyl-tert-butyl ether), a standard TEA solution, generally containing 11 high common explosives (EGDN, 2-NT, 3-NT, 4-NT, NG, 2,4-DNT, 2,6-DNT, 3,4-DNT, 2,4,6-TNT, PETN and RDX) at low concentrations (between 0.1 and 0.75 ng/μL) analysed before and after the sample, three different types of columns – dimethylsiloxane (type BP1), 5% diphenyl-dimethylsiloxane (SGE type BP5) and 7% cyanopropyl-7% phenyl-1% vinyl-dimethylsiloxane (type CPSIL-19) –for GC and confirmation when possible by GC with MS. The markers that were commonly used to provide reference peaks in GC analyses were 2-fluoro-5-NT and the fragrance musk tibetine (2,6-dinitro-3,4,5-trimethyl-tert -butylbenzene). Hiley [42] used the GC– TEA system in these conditions to study chemical analysis methods for post-explosion investigation and in particular those methods developed by the FEL’s Chemical and Electronic Sector and applied to explosive incidents on the UK mainland. The paper focuses on the importance of promptly collecting, analysing and identifying samples of material that are not visible to the naked eye, if the investigation is to be satisfactory. He reports that the systems will detect at worst 50 pg per 0.8 μL injection of the major explosives, which corresponds to about 6 ng in a 100-μL sample.

The presence of dinitrosopentamehylenetetramine (DNPMT), a potential interference in the detection of explosive traces, was revealed in samples taken from a soft suitcase using GC–TEA [43]. This compound is widely used as a chemical blowing agent in the manufacture of foamed polymers and, when analysed by GC–TEA, produces a strong response that might incorrectly be taken as indicative of the presence of PETN or RDX. For GC–TEA analysis, ‘UNICEL 100’ (DNPMT) was used and, for purposes of comparison, the mixed standard solution (TEA standard) containing a low concentration of the common high explosives was used. The pyrolysis furnace was held at 750°C and directly connected into the reaction chamber. In comparison with chromatogram of the TEA standard, the chromatograms of the DNPMT solution showed strong sharp peaks. The FEL standard method for explosive trace identification by GC/TEA required that the relative retention times of the suspect explosive peak and standard explosive peak agreed within ±0.5%. Under this criterion, DNPMT did not coincide sufficiently with PETN or RDX. Nevertheless, the author concluded that GC/TEA analysis with columns of a similar polarity to those used in the study would incorrectly consider DNPMT as indicative of the presence of PETN or RDX.

In another FEL study, Crowson et al. [44] carried out a survey to determine the background level of explosive traces in public places. Samples were taken at various transport sites (buses, taxis, underground trains, passenger aircraft, etc.), and police sites were also sampled to assess how likely it is that a suspect could be contaminated. A pyrolysis oven temperature of 750°C, an interface oven temperature of 250°C and a reaction chamber pressure reading of 0.5–2 mm Hg were the instrument settings. Although the most common high explosives can be detected by the technique in question, the explosive cyclotertamethylene tetranitramine (HMX) and the propellant ingredient nitrocellulose are not sufficiently volatile to be detected. Limits of detection for the complete procedure were estimated for the explosives NG, TNT, PETN and RDX in both clean and dirty samples using the three columns mentioned above. In the case of the BP-5 column and clean samples, the limits of detection (ng) were 1.0, 1.1, 2.2 and 0.6. The results of this survey led the authors to conclude that traces of high explosives were rare within the general public environment. In fact, no traces of NG, TNT or PETN were detected at any of the public sites sampled during this project. Only four low level traces of RDX were detected. Therefore, they concluded that it was unlikely that a member of the public would be innocently contaminated with a significant quantity of