Recent Advances in Trace Explosives Detection

Sens Imaging (2007) 8:9–38
DOI 10.1007/s11220-007-0029-8
ORIGINAL PAPER
Recent Advances in Trace Explosives Detection

Instrumentation
David S. Moore
Received: 3 January 2007 / Accepted: 6 March 2007 / Published online: 26 May 2007
© Springer Science+Business Media, LLC 2007
Abstract There has been a huge increase in instrument development for trace detection
of explosives in the past 3 years. This is especially true for methods that can be used at
a stand off distance, driven by the frightening increase in the use of improvised explosive
devices in both suicide and road side bombings. This review attempts to outline and enumer-
ate these recent developments, with details about the improvements made as well as where
further improvements might come.
Keywords Trace detection · Trace analysis · Explosives · Trace analytical instrumentation ·

Reviews
1 Introduction
The inventiveness and creativity of those that would do the civilized world harm are seem-
ingly limitless. This fact has been true throughout history; today is no exception. While
civilized people might have difficulty understanding their enemies’ motivation, they can and
must use their own creativity to proactively conceive adequate defenses. The most recent
alarming increase in number and violence of terrorist bombings has made the task of stand-
off detection of improvised explosive devices extremely urgent. Yet, because of the variety
of explosive materials available, cleverness of packaging, variability of venue, and the
(mostly) low vapor pressures of explosives, the task of detection is extremely difficult.
This review is intended to highlight recent advances in analytical instrumentation and
methodology applicable to trace, vapor, and stand-off explosives detection. It is also intended
to compare current capabilities to what is necessary for field use. As was the case with my
earlier review [1], the focus here will be on results published in the archival scientific lit-
erature, via both peer reviewed journals and proceedings volumes (and also some National
Laboratory reports), rather than vendor information.
D. S. Moore (B)
Shock and Detonation Physics Group, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
e-mail: moored@lanl.gov
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10 Sense Imaging (2007) 8:9–38
2 Properties of Explosives
The attributes of an explosion are: a chemically or structurally unstable molecule or mixture,

a rapid rate of reaction, a large amount of heat generated, and a large fraction of gaseous
products so that the reaction produces large changes in pressure. These attributes are also
characteristic of fuels and oxidizers; what differentiates explosives is their ability to not react
until initiated by shock or heat applied to a small volume, which expands rapidly through
the material. A rapid decomposition (deflagration) without formation of a shock wave is
characteristic of a low explosive. Lack of shock formation is ideal (even critical) for use of
energetic materials as propellants. High explosives support a leading shock (the detonation
front) at velocities from 1 to 9 km/s. In certain circumstances, a high explosive only reacts
at low order. Such circumstances might include small diameter charges (below the failure
diameter) or low density. The sensitivity to impact, friction, and heat differentiates primary
from secondary explosives. While a typical high explosive has fuel and oxidizer in the same
molecule, other materials also yield large amounts of energy and gas in a very short time and
have therefore been exploited by terrorists. Even primary explosives (those whose initiation
characteristics make them difficult to handle safely) have been used (e.g., TATP, HMTD, NG).
Intimate mixtures of fuels and oxidizers are common (e.g., ANFO, slurries, black powder).
Oxley and Smith have recently provided a relevant overview of the properties of peroxide
explosives [2].
The number and kinds of explosive materials utilized recently has necessitated more basic
studies on their properties, including those properties relevant to their detection. In particu-
lar, a number of new studies of vapor pressure have been published [2–6]. These have been
incorporated into Fig. 1, revised and updated from Figure 1 of Reference 1. Some common
explosives missing from the earlier figure have been added (NM, H2 O2 , TATB, DATB, NG,
TNM) [3–6]. Fortunately, most of the newly utilized materials have significant vapor pres-
sures, reducing the difficulty of vapor phase detection. On the other hand, traces of explosive
materials on the exterior of packaging disappear more quickly for higher vapor pressure
materials [7,8], so that methods relying on swipes or surface treatments may have a time
dependence not seen for lower vapor pressure materials. Studies of other properties specific
to detection methods are discussed in each section below.
There have been a number of studies of source term dynamics and vapor transport. The
transport of explosive vapors from buried landmines (which could be equated to buried IEDs)
has been modeled as a diffusion process, with detection scenarios based on statistical models
[9]. The diffusion process can be strongly perturbed by turbulent atmospheric flows, caus-
ing large fluctuations in concentration with space and time. In addition, packaging plays an
extremely important role in concealing explosives [1]. Information on common methods used
to mask the presence of IEDs has been presented in a concise paper by Turecek [10].
3 Recent Reviews
A large number of workshops and conferences have been held in the past 3 years that are rele-
vant to trace detection of explosives [see Conference References]. New terahertz technology
and methods were presented at SPIE conferences on terahertz for military and security appli-
cations. The coupling of sensors with command, control, communications, and intelligence
technologies was the subject of SPIE meetings in 2004, 2005, and 2006. Many overlapping
technologies were discussed in the SPIE meetings on detection and remediation technolo-
gies for mine and minelike targets. NATO Advanced Research Workshops have been held to
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Sense Imaging (2007) 8:9–38 11
Fig. 1 Vapor pressure versus temperature curves for a number of common explosives and related materials.
The solid lines are the experimentally measured temperature ranges; the dashed lines are extrapolations
spawn new ideas and review progress to date. Many new small companies and/or consortia
have been formed to investigate and/or exploit promising new technologies. All of this activ-
ity is a direct consequence of the urgency of this detection problem. Nevertheless, a silver
bullet has not been found, nor is there one on the horizon.
A number of reviews have been hidden within larger papers [11–16], such as the treatise
on canine detection by Harper et al. [11] and the preview of next generation detectors by
Lareau [12]. Nambayah and Quickenden provided a quantitative comparison of a limited
number of methods based on literature quoted detection limits [13]. There are, however,
concerns with quoted detection limits because of the dearth of standard reference materials.
This void is being filled with the availability of a NIST trace vapor calibrator [17], which will
allow higher accuracy LOD determinations as well as cross-comparability of LOD obtained
on different instruments. In addition, known very small amounts of solids can be produced
using ink jet technology [18] and pneumatically assisted nebulization [19]. Nanometer sized
RDX particles have been prepared using aerosol jet techniques [20]. Given a preparation
protocol for accurate and reproducible size and density, these techniques could be useful to
calibrate trace surface detection methods.
A few larger studies involving multiple detection methods are being undertaken. These
include the BIOSENS project in South East Europe [21] and a Swedish land mine and
unexploded ordnance (UXO) detection project named “multi optical mine detection system”
(MOMS) [22]. While these studies are not specifically aimed at IED detection, the results
should provide valuable insight into what works in a variety of situations.
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Fig. 2 Trace vapor and surface explosives detection methods, arranged according to sampling protocol;
includes commercial, in development, and conceptual methods
The remainder of this review is organized like Fig. 2, where the methods used to detect
and identify explosives are arranged by the sampling protocol used. Surface sampling is
divided into contact and non-contact methods. The non-contact methods are divided into
those that have achieved or are capable of stand-off usage and those that can be classified
as “near-field” where the sample actually has to pass through the instrument to be detected.
Contact sampling is divided into swipe, in-place, and vaporization methods depending on
whether swipes are used to sample a surface, a reagent is sprayed onto the surface, or some
means is used to volatilize the material on a surface. Some methods have been demonstrated
for more than one sampling protocol. The discussion below begins with sampling issues and
solutions for both surfaces and vapors. The abbreviations and acronyms are defined in the
glossary.
4 Sampling and Preconcentration
Because vapor phase concentrations of most explosives are so low, sampling and preconcen-
tration are necessary to achieve reasonable ROC (receiver operating characteristic) curves,
which allow comparison of detection methods on an equal playing field, on the basis of their
sensitivity and selectivity (specificity) [16]. ROC curves can be brought closer to the ideal
by improving the magnitude of the signal change with/without analyte, or by reducing mea-
surement error limits. One way to achieve the former is by increasing the amount of analyte
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by improved sampling or preconcentation. A large number of sampling and preconcentration

methods have been previously reviewed [1,12].
4.1 Sampling
Standard sampling methods have been used for explosives, especially for environmental
studies [23]. Samples have been obtained using extraction methods such as supercritical
fluid extraction [24], solid phase extraction [25], and solid-liquid extraction [26]. Swipes
have been used to determine surface contamination, using new materials such as PTFE
[27]. The efficacy and reproducibility of swipe sampling has been studied and various pro-
tocols compared [28]. For liquid samples, Lokhnauth and Snow have used a variation of
solid phase extraction, termed stir-bar sorptive extraction (SBSE) wherein the SPE phase is
attached to a stir bar, which provides improved solvent contact and better phase ratio (vol-
ume of solvent/volume of coating), and therefore improved recovery and lower detection
limits [29].
At the border between sampling and preconcentration lies a new method involving SPE
of large air volumes followed by SFE extraction and GC separation and detection of the
explosive [30]. High vapor pressure explosives can be sampled directly in the air using
bottles filled with extraction fluids and air sampling pumps [31].
A promising method to actively desorb explosives from surfaces has been demonstrated
using a high power strobe lamp [32]. Another novel method, which has been used to detect
landmines but not yet been demonstrated to desorb explosives, is time reversal acoustic
focusing [33]. These and similar techniques take advantage of the stickiness of most explo-
sives, which concentrates them on environmental or man made surfaces. The sudden large
vapor concentration above the surface caused by flash desorption would allow detection using
a variety of other methods. This area needs considerable new research and development.
4.2 Vapor Concentration Methods
Various materials have been explored for their abilities to adsorb explosive molecules from
the air. Cooks and his colleagues have a number of schemes, including single sided mem-
brane introduction MS, where the same side of an absorbant membrane material is exposed
to the air and then to the mass spectrometer, avoiding the analyte losses and time penalty
seen in two sided MIMS [34]. Kannan et al., have performed a number of studies of polymer
materials such as carbowax and poly(dimethyl siloxane) (PDMS) as adsorbing surfaces for
SAW detection devices [35,36]. PDMS has also been used as a solid phase microextrac-
tion (SPME) preconcentration front end for ion mobility spectroscopy [37]. On the more
esoteric, but perhaps very useable, side, Oxley and coworkers showed that hair, especially
black hair, is a very good explosive vapor sorbent and can be used to indicate exposure
and/or handling [38,39]. Finally, aircraft boarding passes have been used as sampling de-
vices, with desorption performed using short wave infrared radiation and detection via MS
techniques [40].
Many trace preconcentration methods have been developed for environmental monitoring
of explosives contaminated sites [41]. These include the entire range discussed above, but
most commonly SPE [42]. All of these methods can be exploited for preconcentration of trace
explosives for detection and identification, but their utility depends on conduct of operations
limitations.
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4.3 Calibration and Testing Protocols
The US National Academies have called for improvements in sensitivity, selectivity, and
comprehensiveness of explosives detection technologies, as well as verification standards.
The lack of such standards has led researchers to provide their own, with more or less success
and no chance of validation. For example, Thundat and colleagues utilized a calibrated vapor
generator for PETN and RDX using ambient air flowing through a thermostated reservoir
[43,44]. Holl has described several methods in use at the Bundeswehr Research Institute
[45]. To help fill this standards void, Gillen and colleagues at NIST have developed a new
method to provide calibrated trace vapor concentrations of explosives [17]. The method
uses piezoelectric nozzles and a nonporous ceramic-coated platinum resistance temperature
detector element to produce known calibrated concentrations of explosives in an air stream.
By varying solution concentrations in the six-nozzle array, droplet injection rates, air flow,
and the number of active nozzles, the system can provide continuous vapor concentrations
over more than six orders of magnitude, from less than 1 pg/L to 1 µg/L. The availability
of such a calibrated source will greatly aid future method comparisons and validation. In
addition, some methods to produce known quantities of solids and surface deposits were
discussed above in the recent reviews section [18–20].
4.4 Trace Detection on Surfaces
The extremely low vapor pressures of many explosives, coupled with plume transport stud-
ies that show many orders of magnitude variability in concentration over time at a single
location, or spatial variability at a given time, have caused many researchers to direct their
efforts towards detection of trace amounts of materials on surfaces. The reason is simple—a
5 µm diameter speck of solid RDX explosive has a mass of ∼ 90 pg and contains ∼ 300 bil-
lion molecules, or as many RDX molecules as in 1 L of equilibrium vapor pressure STP air.
A 25th generation fingerprint may contain as much as 100 times this much material. How-
ever, as is the case for vapor detection, the presence of trace explosives on external surfaces
where they can be found and measured depends on the care with which devices are packaged.
For typical IEDs that have been stored for some time, the traces on the exterior may have
evaporated away. On the other hand, other materials could contaminate the exterior from
elsewhere in the storage location. Adding a fuse or trigger mechanism could also produce
exterior contamination. Nevertheless, methods to measure explosives traces on surfaces, and
to distinguish them from background clutter, are in great demand.
Methods recently developed to detect trace deposits on surfaces include colorimetric
chemistry using cymantrene embedded in a polymer and developed using UV radiation [46].
Desorption electrospray ionization (DESI) and desorption atmospheric pressure chemical
ionization (DAPCI) have been used as sensitive and selective ionization methods for MS
analysis of surface materials [47]. Large deposits were found to begin to saturate the DESI
response (> 10 pg), but deposits as small as 1 pg/cm2 of RDX were detectable in positive
ion mode.
Cluster SIMS using C− 8 ions has been used to analyze samples of explosives dispersed as
particles on silicon subtrates. The carbon cluster primary ion was found to greatly enhance
characteristic SIMS signals from the explosives while inducing minimal degradation, allow-
ing high doses rapid spatially resolved molecular information data acquisition [48].
Other spectroscopic methods have been recently used to detect trace surface deposits.
These will be discussed below by method. The advantage of such spectroscopic methods is
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their ability to detect the trace explosives at a stand-off distance. Miziolek and
colleagues have provided an in-depth look at recent progress in laser-based explosives
detection methods [49].
5 Trace Vapor Detection
5.1 Trained Animals
Canines continue to be the gold standard against which other explosives detection methods
are judged. The actual odor chemical(s) that the dogs detect is still a subject of investiga-
tion, although there is significant recent progress [11,50]. In the meantime, other animals are
under investigation. Honey bees have been trained to locate buried land mines and tracked
using LIDAR methods [51], with application to stand-off detection. Moths have also been
trained on explosives odors [52]. A significant body of work has been performed assessing
the capabilities of rats [53–55], which shows detection similar to dogs, smaller size, lower
breeding and housing costs, the possibility of parallel and automated training, and shorter
training times [54,55].
5.2 Separations Methods
A method to detect TATP in ambient air using reversed phase high performance liquid chro-
matography (HPLC) with post column UV irradiation and electrochemical detection was
developed and shown to have a detection limit of 550 ng/L air (sampling 12 L volume) [31].
A similar HPLC, UV photo-assisted electrochemical detection (HPLC-UV-PAED) technique
was used for the detection of trace explosives in ground water and soil extracts [42]. The
vapor pressure of TATP versus temperature was studied using GC/ECD [3]. Holmgren et
al., have determined nitroaromatics, cyclic nitramines, and nitrate esters using LC-MS with
a porous graphitic carbon (Hypercarb) column [56] with improved detection limits ranging
from 0.5 to 41.2 ng. The HPLC methods still suffer from long analysis times (10s of min).
Holmgren et al., used a short column (100 mm) and reduced these times to 3–17 min, however
with loss of separation of some analytes [5].
Direct vapor phase analysis has been performed using gas chromatography. The latest
improvements have come from short high efficiency columns, where the GC analysis only
takes a few seconds. As an example, a 1-m long resistively heated capillary column was
coupled to an uncoated solid-state crystal SAW detector [57]. Heating rates up to 20◦ C/s
produced 10-s chromatograms with peak widths of a few ms. Buryakov uses a multicapillary
gas chromatographic column (MCC) of 1000 longitudinal parallel uniform capillaries each
coated with a stationary liquid phase [58]. Gruznov et al., use the same column type [59]. The
MCC achieves an efficiency of about 15 000 theoretical plates/m. The MicroChemLabTM
from Sandia National Lab [60,61] uses a 86 cm length spiral GC column etched into silicon
(Bosch deep reactive ion etching) 400 µm deep by 100 µm wide and capped with a Pyrex
lid. The total chip area used is < 1.5 cm2 . The design permits rapid heating rates (6.5◦ C/s)
at 3.8 W; faster with more heating power. The chips can be stacked if longer runs are needed.
Detection has been demonstrated using arrays of SAW devices with different coatings, sus-
pended membrane micro hotplates, or micron scale cylindrical ion traps fabricated from
molded tungsten. Explosives vapors can be collected and preconcentrated (MicroHoundTM )
and then desorbed into the MicroChemLabTM for analysis [62,63].
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Other lab-on-a-chip microfluidic efforts for HE detection include an integrated collec-

tion, preconcentration, and analysis system that utilizes electrowetting transport with analyte
concentrations measured by microscale colorimetric techniques [64] and a fully automated
version of this device shown capable of detecting TNT at the 12 µg/mL level in liquids [65],
but the analysis takes 5 min. There have also been a number of new microchip electrophoresis
devices, which have been recently reviewed by Pumera [66].
5.3 Nanotechnology
The border between MEMS devices and nanotechnology for detection devices is becoming
increasingly blurred.
Larsson and colleagues demonstrated a novel biochip for TNT detection using self-assem-
bled monolayers (SAMs) of hydroxyl-terminated oligo(ethylene glycol)-thiols containing
three different TNT analogues in different proportions and either surface plasmon resonance
(SPR) or quartz crystal microbalance (QCM) transduction [67]. The detection limit was
found to fall in the 1–10 ng/mL range in liquids, and the analysis times were 100–400 s. An
alternative transduction scheme uses field effect transistors (FET) based on organic materials.
The binding of nitroaromatic molecules to the thin organic films, which form the transistor
channel, increases the film conductivity and thereby the transistor electrical characteristic,
which amplifies the signal [68]. Patel and collaborators use functionalized polymer-coated
micromachined capacitors to measure the dielectric permittivity of selectively-adsorbed
analytes [69].
An optical fiber based explosives detector based on defect free zeolite films grown on
the straight cut face of a standard communication optical fiber [70] utilizes changes in the
sensor reflectivity on exposure to materials of the size and shape dictated by the zeolite pores
to measure concentration. Selectivity has not yet been demonstrated. Analysis times were
ca. 200 s.
Nanosized molybdenum hydrogen bronze reacts with TATP causing a color change from
dark blue to yellow. The color change can be used in neutralization titrations as well as for
detection [71]. Quantum dots have also been used to detect TNT [72]. The dot (CdSe with a
ZnS shell) fluorescence was excited off resonance using 100 fs pulses at 400 nm (frequency
doubled Ti:sapphire). The fluorescence was observed to shift and quench with added TNT
(in solution at 1 ppm).
Nanocrystalline porous Si films have been used to detect adsorbed nitroaromatic com-
pounds at the ppb by volume level in flowing air via photoluminescence (PL) quenching
[73]. Germanenko et al., took this idea further and measured the PL quenching and decay
dynamics in Si nanocrystals [74]. Their results provided evidence for electron transfer from
the Si conduction band to the LU orbitals of the quenchers, and support a PL model involv-
ing surface states in quantum confined Si nanomaterials. Much work in this area remains
to be done.
5.4 Microcantilevers
Microcantilevers have a unique and extremely sensitive sensing mechanism through their
bending. Their high surface to volume ratio allows surface analyte interactions to induce
large surface forces. Restricting those forces to just one surface using selective coatings
results in differential stresses that cause the cantilever to bend. Microcantilevers are true
MEMS devices and hundreds of sensors can be accommodated on a single MEMS chip.
The recent advances have been made in the technology used to detect the bending and avoid
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use of the typical laser bouncing off the microcantilever tip. Pinnaduwage and collaborators
make use of commercial piezoresistive microcantilever arrays [75]. They coated one of the
microcantilevers with a SAM of 4-mercaptobenzoic acid as a hydrogen bonding coating
for the analytes. They achieved LOD in the low parts per trillion range, but not selectivity
between analytes yet. They do rely on diffusion of the analyte to the detector and the sticking
coefficient, so analysis times can be seconds to minutes.
Nanoporous coatings have been demonstrated to produce micrometer scale bending
responses in the presence of vapor phase TNT, 1-MNT, and 2,4-DNT [76]. They found a
noise-limited detection limit for TNT of 520 parts per trillion (by volume; pptv). Li et al.,
utilized piezoresistive elements constructed from thin single-crystalline silicon and fully
encapsulated by SiO2 and coated with a functionalized SAM to produce a portable micro-
cantilever TNT detector [77]. They measured a detection limit near 20 pptv. Voiculescu and
collaborators designed and fabricated a resonant microcantilever beam in CMOS technology
with piezoresistive transduction [78]. Metalloporphyrins have been used as a sensing surface
material for nitroaromatics in a quartz crystal microbalance sensor [79].
Several groups have adapted microcantilevers or other microscale thermal devices to detect
explosives via deflagration or nanocalorimetry. Pinnaduwage and colleagues detected TNT
deposited on a pulse-heated piezoresistive microcantilever via deflagration induced bending
and resonance frequency shifting [80,81]. Explosive vapors were found to have responses
different from interferents such as water or alcohol. They also used a similar device to measure
the desorption characteristics of various explosives and common inerts [82]. Liu et al., are
developing a nanocalorimetry system using a microreactor for application to rapid screening
of energetic materials at low cost [83].
6 Ion Detection Methods
6.1 Mass Spectrometry
Mass spectrometric methods continue to lead the field for selectivity and sensitivity. Some of
the MS methods also achieve short (ca. 5 s) analysis times by reducing or eliminating sample
preparation. Work has been aimed at new sample introduction methods, improved portabil-
ity, and size and cost reductions. A method based on liquid chromatography electrospray
ionization mass spectrometry in negative ion mode using organic acid adduct ion detection
for quantitative HMX analysis was developed by Pan et al., [84]. They achieved an LOD of
0.78 pg for HMX in solution and a linear calibration curve from 0.5 to 50 µg/L. Cooks and
colleagues have explored desorption electrospray ionization (DESI) mass spectrometry for
detection and identification of RDX, HMX, TNT, PETN, C-4, Semtex-H, and Detasheet on
surfaces [47]. They demonstrated enhancement of the method when reactive additives are
included in the spray solvent, which produce ionic adducts of the explosives. They then used
the method to detect TATP on paper, brick and metal surfaces via alkali metal ion complexa-
tion and collision induced dissociation [85]. LODs were reported in the 1–50 ng range. Most
recently, the use of the method at stand-off distances up to 3 m from the mass spectrometer
has been reported [86]. The University of Puerto Rico at Mayaguez group has used TOF MS
to measure the kinetic energy distributions of NO and NO2 UV photofragmentation (266 nm
100 femtosecond pulses at 500 Hz) products from TNT crystals, TNT vapor, and TNT in
sand [87]. The differences observed could perhaps be utilized to detect and identify energetic
materials. Martin et al., have applied single-particle aerosol mass spectrometry (SPAMS)
to identification of micrometer-sized single explosive particles [88]. They used 7 ns pulses
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at 266 nm to vaporize and ionize the particles, and two reflectron-TOF mass analyzers in
opposite directions to simultaneously detect positive and negative ions.
Methods to increase the efficiency of sample introduction into the mass spectrometer are
also being investigated. Gillen and his collaborators have explored the use of C− 8 carbon
clusters in secondary ion mass spectrometry (SIMS) to reduce sample degradation [48]. Sec-
ondary electrospray ionization (SESI) has been used to detect adduct ions of RDX, NG, and
PETN. Using a nonvolatile adduct-forming agent led to large improvements in detection
limit, down to 5 µg/L for aqueous solutions of RDX [89]. Both femtosecond and nanosec-
ond laser photoionization has been used to sensitively detect TATP using time-of-flight mass
spectroscopy. A much larger fraction of parent and high mass fragments were obtained using
the 130 fs pulses at 795 nm wavelength compared to 5 ns pulses at 266 nm and also to electron
impact ionization [90]. This same group then explored the advantages of single-photon ioni-
zation for TOF-MS detection of nitrobenzenes and nitrotoluenes [91]. The required 118.2 nm
photons were produced by focusing the 30 mJ third harmonic (355 nm) output of a 5 ns pulse
length Nd:YAG laser into a gas cell containing Xe or Xe/Ar mixtures to achieve frequency
tripling. The single photon ionization resulted in nearly complete parent ion plus parent-OH
ion species, with very little fragmentation, giving LOD in the 10–50 ppbv range in air.
The large resonance electron capture cross sections at low electron energies of nitro-
gen rich compounds has been taken advantage of using a tunable energy electron mono-
chromator (TEEM) as the ionization source in GC/MS. The TEEM allows tuning of the
ionization energy while monitoring electron capture resonances in real time, with resulting
detection limits as low as 175 fg (TNT) [92]. Stamboli et al., have used headspace-GC-ion trap
MS to detect TATP. The LOD after optimizing all experimental parameters (especially for
low thermal decomposition) was found to be 0.1 ng using injections of 1 mL of headspace
gas [93].
6.2 Ion Mobility Spectrometry
IMS appears to be a mature technology with many commercial instruments in place for trace
HE detection. Analysis is by vapor sampling or swipes, and takes less than 1 min in most
cases. Denton et al., showed that these commercial instruments should be modified to detect
positive as well as negative ions in order to permit efficient detection of peroxides [94]. They
also found that the presence of toluene dramatically improved the detection limit for TNT to
187 µg/mL. Clowers et al., have developed an IMS system that improves the duty cycle to
50% by the use of Hadamard transform techniques [95]. The Hadamard transform method
improved the signal to nosie ratio by factors of 2 to 10 without reducing the instrumental
resolution. Sandia National Lab researchers have assembled and are testing RobohoundTM ,
a robotic platform with manipulator arm, chemical sampling, and a commercial IMS explo-
sives detector [96]. Given the extensive numbers of IMS units presently in use, Wallis and
collaborators have developed a field performance and maintenance protocol to help ensure
their correct operation over a wide range of field conditions and extended usage times [97].
7 Vibrational Spectroscopic Methods
Some of the greatest improvements in explosives detection during the past 3 years have been
made in the area of vibrational spectroscopy. This statement is especially true if we include
THz spectroscopy in this area. Several of these methods have been shown capable of detect-
ing explosives on surfaces at stand-off distances, although much work remains to be done to
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improve selectivity and differentiation from matrix effects and background clutter. A large
fraction of energetic materials contain -NO2 groups, whose vibrational signatures are very
characteristic. As an aid to further application of vibrational spectroscopic detection meth-
ods, Beal and Brill have provided a comprehensive treatise on the behavior of the vibrational
spectra of the -NO2 group in more than 50 energetic compounds [98]. They also note that
the insensitivity of the scissor motion frequencies (842–846 cm−1 ) to differences in the local
chemical environment could enable them to be used as detection tags. Similarly, the presence
of nitro group out-of-plane deformation bands within the range 760–767 cm−1 could be used
in a similar way.
7.1 Infrared Absorption Spectroscopy
There have been a few advances during the past 3 years in gas phase absorption methods for
detection of explosives vapors. Willer et al., showed how difference frequency generation
using two narrow band tunable diode lasers can generate narrow band tunable mid infrared,
and demonstrated detection of NO vapor from laser ablation of different trace amounts of
explosives on surfaces [99]. They propose to distinguish between explosives via the time
dependent NO production rate with ablation laser pulse energy, repetition rate, and wave-
length. They also demonstrated a fiber coupled infrared attenuated total reflection (evanescent
wave) device to detect trace atmospheric gases, which could be adapted for explosives vapor
detection given suitable coating materials to adsorb the target molecules.
Other advances in infrared detection of explosives on surfaces have been obtained by
Hernandez-Rivera and colleagues. This group has detected explosives on surfaces using a
fiber-coupled FTIR probe [100], studied the temperature dependence of the limit of detec-
tion of TNT on metallic surfaces using fiber optic couple FTIR [101], detected and classified
explosives mixtures on surfaces using grazing angle FTIR [102], demonstrated laboratory
scale stand-off detection of RDX and TNT on reflective surfaces [103], and characterized
thermal inkjet produced surface deposits of TNT using grazing incidence FTIR [18]. They
have also measured the infrared spectral changes of TNT, RDX, and PETN attached to clay
and other environmental materials [104–106].
A new differential absorption LIDAR (DIAL) system based on mid-infrared tunable
optical parametric oscillators pumped by compact Q switched lasers is intended to detect
nitrocompounds such as TNT, DNT, MNT, and RDX [107]. An IR point sensor consisting
of a solid state IR emitter, polymer sorbent on IR windows and a multispectral IR detector is
under development [108].
7.2 Raman Spectroscopy
Raman spectroscopy has been demonstrated to be capable of stand-off detection of trace

quantities of explosives on surfaces. Some advances in stand-off Raman were reviewed or
presented at the GEORAMAN 2004 conference [109]. Sharma et al., have tested a portable
stand-off Raman system based on a 35 mJ 20 Hz frequency doubled 532 nm Nd:YAG excita-
tion laser, a 125 mm aperture Cassegrain Maksukov telescope (f/15), an f/2.2 spectrograph
with 100 µm slits, and a gate intensified CCD detector. The Raman signal collected by the
telescope was filtered from the Rayleigh scattered excitation using a notch filter. The filtered
Raman signal was passed to the spectrometer either using optical fibers or by direct optical
coupling. The direct optical coupling method was found to be about 10 times as efficient (for
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their optical parameters). They have used their system to detect mg quantities of HMX and
TATB at a distance of 10 m [110]. Carter and collaborators extended this range to 50 m using
a 200 mm aperture f/11 Schmidt-Cassegrain telescope and a higher power frequency doubled
Nd:YAG laser (up to 140 mJ) [111]. Sharma et al., have demonstrated 100 m stand-off Raman
using using direct optical coupling of the 125 mm aperture telescope to the spectrograph, but
not on explosives samples [112]. All of these studies utilized signal-averaged spectra from
multiple laser shots (several hundred) to achieve sufficient signal to noise to discern the
explosives samples. This signal averaging implies data accumulation times of > 10–100 s
with present technology for fingerprint sized samples at > 10 m stand-off.
Carter et al., have also compared conventional grating based and acousto-optic tunable
filter based spectrometers for stand-off Raman signal to noise and throughput [113]. In their
study, the fiber optic coupling apparently limited the signal level, so that the larger AOTF
aperture could not be adequately utilized. The AOTF system’s capability to provide Raman
imaging at stand-off distances (by tuning the AOTF to the wavelength of an appropriate
Raman resonance) was demonstrated using non-explosives. They also measured the opti-
mum ICCD gate width for the AOTF based system, which was found to be 2 µs (1 µs widths
were found to be problematic due to laser/ICCD gate pulse timing jitter).
A major issue with the use of Raman spectroscopy to detect explosives is that of back-
ground clutter, not only in the form of fluorescence, but also from Raman signals from matrix
materials or surfaces. Fluorescence interference can be reduced but not eliminated by mov-
ing to redder excitation wavelengths. This tactic suffers from dramatically decreased Raman
cross sections (which vary as ν 4 in wavelength ranges without electronic excitations), and also
run up against the limitation of silicon based detectors (whose efficiency drops dramatically
above 1000 nm). Alternatives are to use InGaAs or other near-infrared detector materials and
suffer the ν 4 penalty, or to move into the UV where both the ν 4 improvement and electronic
resonance enhancements provide much larger Raman signal strength [114,115]. Lewis et al.,
have compared Raman spectra of a variety of energetic materials at three different excitation
wavelengths: 785, 830 and 1064 nm [116]. For the 1064 nm excitation, anti-Stokes Raman
spectra were recorded [117]. The signal to noise and Raman peak to fluorescence intensi-
ties were measured in each material at each excitation wavelength, with the conclusion that
830 nm excitation is the best compromise for a field-portable instrument. Their other conclu-
sion, however, was that Fourier-transform Raman using 1064 nm excitation and a portable
FT spectrometer is an exciting future possibility with the recent introduction of a < 20 kg
commercial system.
Fluorescence interferences have been reduced using both photobleaching and background
subtraction methods [118,119]. Photobleaching uses extended illumination of the sample,
which serves to bleach fluorescent compounds if trap states are available. Such a method
will have difficulty in applications involving short illumination time stand-off detection. A
variety of baseline removal (background subtraction) methods have been used. Noonan et
al., measured the background fluorescence spectrum in separate experiments and subtracted
that spectrum from the Raman plus fluorescence spectrum [118].
Alternatively, Hasegawa et al., utilized the photobleaching phenomenon coupled with
principal component analysis to separate the Raman spectrum from the fluorescence back-
ground [120]. Ben-Amotz and coworkers demonstrated a method based on second-derivative
variance minimization, but it requires a priori measurement of the background or interfer-
ences [121]. The baseline can be fit and removed manually by picking points and using
spline segments or polynomials, as is done in much commercial spectroscopic software. The
accuracy and precision of such manual baseline removal methods has been analyzed [122].
Blades and colleagues have provided a quantitative comparison of baseline removal methods,
123
which they classify into methods requiring knowledge of the baseline b, blurring function p
and the noise function n (e.g., maximum entropy method), methods requiring estimates of
the baseline (e.g., neural networks, threshold based classification, signal removal methods,
composite baseline method, spectral shift methods), methods requiring no explicit knowledge
of b, p, or n (e.g., noise median method and first derivative method), and methods requiring
information about frequency (e.g., Fourier transform method, wavelet transform method)
[123]. Each method is compared regarding their strengths, weaknesses, and amenability to
automation, which will be useful for future studies of stand-off Raman of energetic materials
in a variety of matrices and on many different types of surfaces. A newer rolling circle filter
method based on the difference of the radii of curvature of Raman lines and the background
has been successfully demonstrated as long as the widths of the Raman lines are significantly
less than the background bandwidth [124].
7.3 Surface Enhanced Raman Scattering (SERS)
Nobel metal nanoparticles or nanostructures have been observed to cause large enhance-
ments of the Raman signals for adsorbed molecules through a combination of localized
surface plasmon resonance and induced increases in molecular bond polarizability. There
have been further applications of SERS to detection of vapor phase explosive molecules dur-
ing the past 3 years. Spencer and his collaborators used electrochemically roughened gold
and silver substrates to detect the vapor signature over a TNT based landmine, and have
produced a fieldable SERS vapor sensor with volumetric flow rates up to 0.4 L/s, which has
been successfully used to detect landmines [125]. Reproducible and robust SERS substrates
continue to be sought [126], and a large number of methods to achieve this goal have been
recently reviewed [127]. Enhancement of TNT Raman signals on non-noble metal materials
is being investigated [128]. These SERS methods rely on accumulation of the analyte from
the vapor onto the substrate, implying minute range analysis times when diffusion controlled,
or faster if active air movement schemes are utilized.
Smith et al., have continued to explore the capabilities of combining surface enhance-
ment with resonance enhancement [129]. They have used surface enhanced resonance Ra-
man scattering (SERRS) in combination with clever species-specific chemistry to detect and
distinguish explosives in solution. Using azo dyes containing electron-donating moieties for
efficient diazo coupling and strong silver complexing groups to attach the product molecule
to the SERS substrate allowed detection of TNT at near nM concentrations. They have also
incorporated the chemistry into a microfluidics device [130]. Similar SERRS technology was
interrogated at stand-off distances up to 20 m using a commercial portable Raman system
adapted with a telephoto lens (no specifics given) [129].
7.4 Cavity Ring Down Spectroscopy
Cavity enhanced spectrometric methods have been recently reviewed [131]. The Cadillac
implementation of CRDS in the mid-infrared has still not been improved upon [132]. How-
ever, CRDS has recently been made field deployable by using fiber optics and evanescent
wave devices [133]. Evanescent wave cavity ring down utilizes the change in quality (Q
factor) of an optical cavity as a function of the absorbance by species within an evanescent
field. This idea has been implemented in the visible and near IR using a Dove prism lo-
cated in a high Q cavity formed by two high reflectivity mirrors, and diode lasers. The Dove
prism allows the necessary linear light path while providing a total internal reflection for the
123
evanescent wave. A similar concept could be implemented in the mid infrared, but no
references were found.
7.5 Terahertz
The recent spectacular growth of interest in the terahertz region of the spectrum (loosely
defined as the frequency range from 0.1 to 10 THz; THz = 1012 Hz) derives from the capa-
bility of those frequencies to penetrate many non-metallic materials, allowing the possibility
to locate hidden explosives. THz techniques can identify materials via the spectrum of their
absorbance by low frequency molecular motions, similar to infrared absorption methods. The
recent advances include fundamental studies of the THz spectra of target materials as well
as packaging and other matrix materials, technological improvements, exploration of stand-
off detection, and combinations of THz with other methods. Terahertz methods are capable
of rapid detection, i.e., < 1 s, depending on the distance and sample size.
Fundamental spectroscopic studies of explosives include: the measurement of the RDX
transmission spectrum for granular RDX [134]; the THz spectra of 4-nitrotoluene and 2,6-
dinitrotoluene with assignments aided by density functional theory calculations [135]; THz
spectroscopy of granular RDX from 0.3 to 10 THz [136]; and the temperature dependent THz
transmission spectra of oriented single crystals of RDX, HMX, and PETN [137]. Further work
on single crystal materials remains to be done to extract the full polarization dependence.
Time domain THz spectra of RDX, C-4, and ammonium nitrate were compared to long wave
FTIR spectra by Huang et al. [138]. Imaging and spectroscopy of the plastic bonded explo-
sives PBX 9501 (HMX based) and PBX 9502 (TATB) were measured near 1 THz by Funk
et al., [139]. Burnett et al., have measured THz spectra of PETN, TNT, and RDX in polymer
matrices as well as pure, and have presented the temperature dependent spectra of PETN and
RDX [140]. They also measured THz spectra of two plastic bonded explosives, Semtex-H
(a mixture of RDX, PETN, plasticizers and dyes) and SX2 (contains RDX), and compared
THz spectra to Raman spectra of the materials. There are many more explosives whose THz
spectra need to be measured.
THz methods have been used to detect and identify explosives. Yamamoto et al., exam-
ined the ability of THz time domain spectroscopy (TDS) to detection C-4 in mail items
[141]. THz pulsed spectroscopic imaging was used to detect and identify RDX using seven
absorption features in the 0.3 to 10 THz range (5–120 cm−1 ) [142]. They also imaged the
spatial distribution of RDX using reflection THz spectroscopic imaging. The ability to do
THz imaging of specific substances using reflection techniques is crucial for eventual security
screening applications. Other groups have also demonstrated THz reflection spectroscopy.
Fitch et al., demonstrated this capability using specular reflection at 45◦ angle of incidence
and a conventional TDS THz system [143]. The same group has presented results for THz
diffuse reflection detection of RDX [144], and has addressed propagation and imaging of
THz through porous or granular media [145]. Federici et al., discuss in depth estimates of
the effective range, spatial resolution, and portability issues necessary for stand-off THz
imaging and detection [146]. De Lucia presented a series of enabling developments—the
‘X’ factors–needed to firmly establish THz methodology in practice [147].
This basic information has led to the recent demonstrations of stand-off detection of explo-
sives using THz methods. Zhong et al., reported the observation of RDX at distances up to
30 m using its 0.82 THz absorption peak, which lies between the 0.78 and 0.98 THz water
absorption lines [148].
Finally, Lu and collaborators have proposed a THz biochip based on optoelectronic devices
[149]. The device incorporates a membrane-type edge-coupled photonic THz transmitter on
123
a thin glass substrate with integrated polyethylene channel for near field THz detection of
biomolecules adsorbed in the polyethylene channel. The channel near-field micro detection
concept was shown feasible using standard TDS THz methods.
8 Other Spectroscopic Methods
A variety of ideas utilizing some other kind of optical spectroscopic transduction scheme
has been thrown at the HE detection problem during the past 3 years.
Several groups have adapted optical fiber transducers with explosives sensitive detection
schemes. The silicalite MFI-type zeolite selective explosives absorber discussed above was
grown on the end of an optical fiber, and the explosives were detected using changes in
refractive index (or optical thickness) [67]. Tait and colleagues coated a fiber Bragg grating
with polymer materials, and detected the expansion of the polymer when it adsorbs the target
molecule via the changes in the Bragg grating period [150]. The grating period changes were
detected using rapid tuning of a communication laser between preset locked wavelengths
combined with transmission spectroscopy to locate the Bragg wavelength resonance.
Cao and Zhang [151] have proposed a cataluminescence sensor array based on nanosized
SrCO3 , γ -Al2 O3 and BaCO3 as catalysts for explosive gas mixtures. Cataluminescence is
the emission of light during catalytic oxidation of molecules on a solid catalyst surface.
Several groups have utilized differential reflection spectroscopy to detect trace explo-
sives. Hummel et al. [152] measured the normalized difference between the reflectivities of
two adjacent parts of a specimen in the UV/visible spectral region, and found distinctive
peaks at 250 and 420 nm characteristic for TNT on the surface. The Hernandez-Rivera group
[153] measured the UV/visible absorption/reflection spectra of TNT on various surfaces, at
distances up to 27 feet.
UV absorption methods have been used to detect photofragments and pyrolysis fragments
from nitro functionalities. Beauchamp and Hodyss [154] used UV detection of NO pro-
duced in thermal decomposition of gas chromatography effluent for the sensitive detection of
nitrobenzene (25 ng) and of 2,4-dinitrotoluene (50 ng). Cabalo and Sausa used a 248 nm laser
to photofragment target residues on a substrate, and then a 226 nm laser to photoionize and de-
tect the resulting NO fragment by resonance-enhanced multiphoton ionization (REMPI) [155].
8.1 Fluorescent Polymers
Swager and his collaborators have continued to advance the ability of semiconductive organic
polymers to detect explosives vapors at extremely low levels [156]. Selectivity between explo-
sives and interferents is being improved in the devices via a fundamental understanding of the
energy transport mechanism along the poly(arylene ethynylene) backbone and its response
to polymer structure, assembly architecture, and receptor characteristics [157]. Fisher et al.,
at Nomadics have continued to provide novel packaging and testing of the Fido sensor based
on Swager’s fluorescent polymers. They have recently reported successful detection of sim-
ulated vehicle-borne IED targets using both vapor and swipe sampling [158]. Cross-reactive
chemical sensors using fluorescent polymers with both narrow and broad specificity are being
utilized in an artificial olfactory system for land mine detection [159]. These devices rely
on the transport of trace vapor, but active air movement can produce detection within a few
seconds.
Other groups have jumped into the fray. Lamarque and collaborators have developed
a polysiloxane based refractive index sensor, as well as a fluorescence quenching polymer
123
(N-(2,5-ditertiobutylphenyl)-1,8-naphthalimide functionalized polystyrene) with 60% quan-

tum yield, whose fluorescence intensity dropped by 45% after a 1 min exposure to DNT
vapor [160]. Three different light emitting conjugated polymers (two poly phenylene vinyl-
enes and a poly diphenylacetylene) showed strong fluorescence quenching when exposed to
TNT and DNT vapor [161]. Toal and Trogler investigated luminescent polymers as well as
resistive sensing using polymer-coated carbon black particles and luminescent polymetalloles
for sensing explosives in aqueous solution [162].
9 Immunochemical Sensors
Different transduction schemes have been investigated over the past 3 years to enhance
the ability of immunochemical processes to detect explosives. The Shankaran and Mat-
sumoto groups at Kyushu University have utilized surface plasmon resonance transduction
and indirect competitive immunoreactions to detect TNT vapor with excellent detection
limit (60 pptv) and large dynamic range (to 1000 ppbv) [163]. The method utilizes com-
petitive inhibition via two polyclonal antibodies, one prepared from goat [164] and the
other from rabbit [165]. Bowen et al., have also used SPR transduction to detect TNT
in the gas phase at ppbv concentrations via a monoclonal antibody covalently bound to
a SAM attached to a thin gold film [166].
Shriver-Lake and colleagues have developed a continuous flow displacement immunoas-
say biosensor for TNT and RDX, and have used it to detect sub-ppb levels of explosives in
water samples or soil extracts in less than 5 min [167]. They extended similar ideas to pro-
duce an array biosensor for simultaneous multi-analyte detection [168]. The array is based
on a planar waveguide patterned with small sensing regions and end-illuminated by a 635 nm
diode laser via a line generator. The emitted fluorescence is imaged onto a cooled CCD
camera, which provides detection limits similar to those obtained from standard ELISA.
Charles et al., described a reversed-displacement immunosensor for TNT using a chem-
ically modified glass capillary [169]. The device achieved a detection limit of 0.25 µg/L
for TNT in seawater with analysis time under 5 min. A portable flow-injection immuno-
sensor utilizing chemiluminescence inversely proportional to the analyte concentration has
been shown capable of detecting below 0.1 µg/L TNT in the laboratory with analysis times
under 10 min [170]. The important factors in this instrument are the competition between the
analyte and the enzyme-tracer, the luminescence background signal, and the flow pattern
inside the chip. Lee et al., used a set of antibody coated SAW resonators inside a flow
cell to detect TNT and RDX vapors from plastic explosives [171]. A non-specific reference
sensor was employed to minimize environmental effects and interferences. Finally, proxim-
ity-induced fluorescence resonance energy transfer of antibody labeled quantum dots was
used to detect TNT in aqueous environments [172].
10 Electrochemical Sensors
The wide variety of electrochemical processes have continued to be refined for lower explo-
sives detection limits and better selectivity. As is the case for many of the other methods, new
materials have been explored and exploited. Zhang et al., have investigated cathodic voltam-
metry using mesoporous SiO2 (MCM-41) modified glassy carbon electrodes, which showed
nanomolar detection limits for TNT, TNB, DNT, and DNB [173]. The improved sensitivity
123
over previously investigated electrode materials was attributed to the strong adsorption of
nitroaromatic compounds by MCM-41 and the large electrode working surface area. An
electrochemically preanodized screen-printed carbon electrode was found to sharpen the
reduction peak and thereby improve substituent selectivity [174]. The analysis can be done
in a single-run measurement simply by measuring the peak current ratio between analytes
and an internal standard. Hrapovic and collaborators formed nanocomposites of metal nano-
particles together with carbon nanotubes (CNT) solubilized in Nafion for cyclic voltammetric
detection of TNT and other nitroaromatics [175]. The best combination was a modified glassy
carbon electrode (GCE) containing Cu nanoparticles and single walled CNT, with a repro-
ducible TNT detection limit of 1 ppb and 3 order of magnitude linear dynamic range. Wang
et al., have used GCE modified with multi-wall CNT to detect TNT at the sub-µg/L level by
adsorptive stripping voltammetry with 10 min deposition times [176].
Masunaga et al., utilized a surface-polarization controlling method to measure electro-
chemical impedance, as well as an anthracene treated electrode surface, to improve the
selectivity between aromatic nitro compounds [177].
The Wang group at NMSU has made several advances in electrochemical detection of
explosives. Wang has reviewed several types of microchip devices from his group and oth-
ers [178]. They have fabricated an amperometric detection system from a CE microchip
and a disc detection electrode in a Plexiglas holder [179]. The holder facilitates the precise
3-D alignment between the CE channel outlet and the detection electrode without a 3-D
manipulator. The system was tested using a mixture of four nitroaromatic pollutants, and the
optimized separation time was < 2 min with limits of detection down to 12 ppb. They have
also produced a remote underwater electrochemical sensing system to detect TNT in aque-
ous environments [180]. The system utilizes a carbon fiber working electrode and square
wave voltammetry, mounted on a remotely operated surface vehicle with vision capabil-
ities and wireless communication. Finally, they have developed a voltammetric method to
detect the explosive taggant DMNB (2,3-dimethyl-2,3-dinitrobutane) with 60 µg/L detection
limit [181].
11 Conclusions
There have been many improvements on nearly every analytical methodology to prove their
abilities to detect explosive traces and vapors at the lowest possible detection limits, at the
furthest possible stand-off distance, and in the shortest possible time. There are still many
areas where great improvements are possible, and which will be necessary to provide the
detection tools adequate for the task as well as for routine field use.
For example, to date only LIBS and Raman have been demonstrated to detect fingerprint
size explosives samples at significant stand-off distances (> 10 m). The fluorescence problem
for stand-off Raman detection of explosives on real-world surfaces is being attacked using
deep UV excitation as well as time-gating techniques, but significant signal accumulation
times (ca. 100 s) are required for very small mass samples. LIBS has been demonstrated able
to detect fingerprint sized explosives residues on a car door at 30 m distance, with ca. 1 s data
accumulation times. Terahertz methods have achieved great advances in the past few years,
and show some promise for stand-off detection of surface contamination. A large amount of
basic THz spectroscopy work is still needed on these materials. However, these and other
surface contamination sensors rely on the sloppiness of illicit weapon manufacturers.
Fluorescence amplifying polymer based explosive sensors have been widely deployed and
tested, and as new sensing materials are developed for a greater variety of explosives, the
123
method will continue to improve. All trace vapor point sensors are subject to large concentra-
tion excursions due to turbulent atmospheric flows from the source. Signal integration times
of a few seconds may help smooth out some of these excursions. Also, instrument cost reduc-
tions could allow such devices to be distributed or to provide guidance along concentration
gradients to the source.
Mass spectroscopic methods show great promise, but are still held back from routine
portable application by their size and cost. Ion mobility spectrometry appears to be mature,
but great advances have been made recently in dual tube technology for both positive and
negative ion detection, miniaturization, and data analysis.
The methods reviewed here have shown recent improvements in vapor detection limits,
selectivity, robustness for field application, and stand-off distance. They all still rely on the
uniqueness of some kind of molecular signature for their selectivity, and the vapor detection
methods continue to be plagued by the low volatility of many of the target analytes. Some
schemes have recently been introduced to volatilize explosives attached to surfaces, locally
increasing the vapor concentration and thereby their detection. There are large gains available
in this area. Finally, explosives are unique molecules in one sense—they store considerable
energy and release it “on command.” That unique attribute has not yet been exhaustively
explored for detection.
Acknowledgements This work was performed under the auspices of the US Department of Energy National
Nuclear Security Administration. The author thanks Jim Koster, Scott Kinkead, and David Robbins for support.
Glossary
Explosives
AN ammonium nitrate; NH4 NO3
ANFO composition of ammonium nitrate and fuel oil
AP ammonium perchlorate; NH4 ClO4
C-4 composition of 91 % RDX plus waxes and oils
DADP diacetone diperoxide
DATB diamino trinitro benzene
Detasheet composition of PETN and NC with plasticizers
DMNB 2,3-dimethyl-2,3-dinitrobutane (an explosives taggant)
2,4-DNT 2,4-dinitrotolune
EGDN ethylene glycol dinitrate; nitroglycol
HMTD hexamethylenetriperoxidediamine
HMX octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine; octagen
HNS hexanitrostilbene
H2 O2 hydrogen peroxide
NC nitrocellulose; gun cotton
NG nitroglycerine; nitro; glyceryl trinitrate; RNG; trinitroglycerine
NM nitromethane
NQ nitroguanidine
PBX plastic bonded explosive
PBX-9501 plastic bonded explosive with HMX
PBX-9502 plastic bonded explosive with TATB
PE-4 British Comp C: RDX with waxes and/or heavy oils
PETN pentaerythritol tetranitrate; 2,2-bis[(nitroxy)methyl]-1,3-pro-
panediol, dinitrate
123
Picric acid 2,4,6-trinitrophenol

RDX hexahydro-1,3,5-trinitro-1,3,5-triazine; cyclonite; hexogen
Semtex-H composition of RDX and PETN with heavy oils and rubbers
TATB triamino trinitro benzene
TATP triacetone triperoxide
Tetryl methyl-2,4,6-trinitrophenylnitramine
TNM tetranitromethane
TNT trinitrotoluene
Other
AOTF acousto-optic tunable filter
CARS coherent anti-Stokes Raman scattering
CCD charge coupled device
CE capillary electrophoresis
CMOS complementary metal oxide semiconductor
CNT carbon nanotube
CRDS cavity ring down spectroscopy
DAPCI desorption atmospheric pressure chemical ionization
DESI desorption electrospray ionization
DIAL differential absorption LIDAR
ECD electron capture detector
ELISA enzyme linked immunosorbent assay
FAP fluorescence amplifying polymers
FET field effect transistor
FTIR Fourier transform infrared
GC gas chromatography
GCE glassy carbon electrode
HPLC high performance liquid chromatography
ICCD intensified CCD
IED improvised explosive device
IMS ion mobility spectrometry
LC liquid chromatography
LIBS laser induced breakdown spectroscopy
LIDAR light detection and ranging
LOD limit of detection
LU lowest unoccupied (molecular orbital)
MCC multicapillary column
MEMS microelectromechanical systems
MIMS membrane introduction MS
MS mass spectrometry
NATO North Atlantic Treaty Organization
Nd:YAG neodymium doped yttrium aluminum garnet
PAED photo-assisted electrochemical detection
PDMS poly(dimethyl siloxane)
PL photoluminescence
PTFE poly(tetrafluoroethylene)
QCM quartz crystal microbalance
REMPI resonance enhanced multiphoton ionization
ROC receiver operating characteristic
123
SAM self assembled monolayer

SAW surface acoustic wave
SBSE stir-bar sorption extraction
SERS surface enhanced Raman scattering
SERRS surface enhanced resonance Raman scattering
SESI secondary electrospray ionization
SFE supercritical fluid extraction
SIMS secondary ion MS
SLE solid-liquid extraction
SPE solid phase extraction
SPIE the International Society for Optical Engineering
SPME solid phase microextraction
SPR surface plasmon resonance
STP standard temperature and pressure
TDS time domain spectroscopy
TEEM tunable energy electron monochromator
TOF-MS time of flight mass spectrometry
UV ultraviolet
UXO unexploded ordinance
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A. J. Sedlacek III, R. Colton, & T. Vo-Dinh (Eds.) Chemical and biological point sensors
for homeland defense. In Proceedings of SPIE Vol 5269. SPIE, Bellingham, WA.
Edward M. Carapezza (Ed.), Sensors, and command, control, communications, and intelli-
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123
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tions II. In Proceedings of the SPIE Vol. 5411. SPIE, Belllingham, WA.
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diation technologies for mines and minelike targets IX. In Proceedings of the SPIE Vol.
5415. SPIE, Belllingham, WA.
Edward M. Carapezza (Ed.), Sensors, and command, control, communications, and intelli-
gence (C3I) technologies for homeland security and homeland Defense IV. In Proceedings
Michael J. DeWeert & Theodore T. Saito (Ed.), Photonics for port and harbor security.
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Theodore T. Saito (Ed.), Optics and photonics in global homeland security. In Proceedings
R. Jennifer Hwu, Dwight L. Woolard, & Mark J. Rosker (Ed.), Terahertz for military and
security applications III. In Proceedings of the SPIE Vol. 5790. SPIE, Belllingham, WA.
Russell S. Harmon, J. Thomas Broach, & John H. Holloway, Jr. (Eds.), Detection and
remediation technologies for mines and minelike targets X. In Proceedings of the SPIE Vol.
5794. SPIE, Belllingham, WA.
J. C. Carrano, A. Zukauskas, A. W. Vere, J. G. Grote, & F. Kajzar (Eds.), Optically based

biological and chemical sensing, and optically based materials for defense. In Proceedings
of SPIE Vol. 5990. SPIE, Bellingham, WA.
James O. Jensen, & Jean-Marc Thériault (Eds.), Chemical and biological standoff detection
III. In Proceedings of the SPIE Vol. 5995. SPIE, Belllingham, WA.
Edward M. Carapezza (Ed.), Sensors, and command, control, communications, and intel-
ligence (C3I) technologies for homeland security and homeland defense V. In Proceedings
Theodore T. Saito & Daniel Lehrfeld (Eds.), Optics and photonics in global homeland
security II. In Proceedings of the SPIE Vol. 6203. SPIE, Belllingham, WA.
Michael J. DeWeert, Theodore T. Saito, & Harry L. Guthmuller (Eds.), Photonics for
port and harbor security II. In Proceedings of the SPIE Vol. 6204. SPIE,
Belllingham, WA.
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for military and security applications IV. In Proceedings of the SPIE Vol. 6212. SPIE, Belll-
ingham, WA.
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123
Colin Lewis, & Gary P. Owen (Eds.), Optics and photonics for counterterrorism and crime
fighting II. In Proceedings of the SPIE Vol. 6402. SPIE, Belllingham, WA.
M. Krausa, & A. A. Reznev (Eds.), Proceedings of the NATO advanced research workshop
on vapour and trace detection of explosives for anti-terrorism purposes, NATO Science
Series II. Mathematics, physics and Chemistry – V. 167. Dordrecht: Kluwer
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on electronic noses and sensors for the detection of explosives, NATO science series II.
mathematics, physics and chemistry – V. 159. Dordrecht: Kluwer
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detection and disposal of improvised explosives, NATO security through science series – B:
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123

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Sens Imaging (2007) 8:9–38

Recent Advances in Trace Explosives Detection

Keywords Trace detection · Trace analysis · Explosives · Trace analytical instrumentation ·

The attributes of an explosion are: a chemically or structurally unstable molecule or mixture,

4 Sampling and Preconcentration

by improved sampling or preconcentation. A large number of sampling and preconcentration

4.2 Vapor Concentration Methods

4.3 Calibration and Testing Protocols

4.4 Trace Detection on Surfaces

5 Trace Vapor Detection

5.1 Trained Animals

5.2 Separations Methods

Other lab-on-a-chip microfluidic efforts for HE detection include an integrated collec-

6 Ion Detection Methods

6.1 Mass Spectrometry

6.2 Ion Mobility Spectrometry

7 Vibrational Spectroscopic Methods

7.1 Infrared Absorption Spectroscopy

7.2 Raman Spectroscopy

Raman spectroscopy has been demonstrated to be capable of stand-off detection of trace

7.3 Surface Enhanced Raman Scattering (SERS)

7.4 Cavity Ring Down Spectroscopy

8 Other Spectroscopic Methods

8.1 Fluorescent Polymers

(N-(2,5-ditertiobutylphenyl)-1,8-naphthalimide functionalized polystyrene) with 60% quan-

Picric acid 2,4,6-trinitrophenol

SAM self assembled monolayer

53. Mott, M. National Geographic. (2004) http://news.nationalgeographic.com/news/2004/02/0210_040210

Relevant Conference References

J. C. Carrano, A. Zukauskas, A. W. Vere, J. G. Grote, & F. Kajzar (Eds.), Optically based

H. Schubert, & A. Kuznetsov, (Eds.), Proceedings of the NATO advanced workshop on

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