Invited Paper

Explosive detection using infrared laser spectroscopy

J. Hildenbrand, J. Herbst, J. Wllenstein, A. Lambrecht*
Fraunhofer Institute for Physical Measurement Techniques (IPM),
Heidenhofstr. 8, D-79110 Freiburg, Germany

ABSTRACT

Stand-off and extractive explosive detection methods for short distances are investigated using mid-infrared laser spectroscopy. A
quantum cascade laser (QCL) system for TATP-detection by open path absorption spectroscopy in the gas phase was developed. In
laboratory measurements a detection limit of 5 ppm*m was achieved. For explosives with lower vapor pressure an extractive hollow
fiber based measurement system was investigated. By thermal desorption gaseous TATP or TNT is introduced into a heated fiber.
The small sample volume and a fast gas exchange rate enable fast detection. TNT and TATP detection levels below 100 ng are
feasible even in samples with a realistic contaminant background.

Keywords: explosive detection, quantum cascade lasers, infrared spectroscopy, hollow fibers

1. INTRODUCTION

Fast and effective detection of explosives is a key security issue against possible terrorist attacks. Especially at public
places like airports, railway or coach stations efficient detection systems are needed. Usual methods at airport security
checks are wiping carry-on baggage / laptop computers etc. to collect samples which are analyzed subsequently by e.g.
gas chromatography mass spectroscopy (GC-MS); gas chromatography chemoluminescence (GC-CL) or ion mobility
spectrometers (IMS). An alternative is to integrate these instruments into a portal configuration, where dust is collected
from persons or baggage by air streams and filters. Clogging of the filters by ordinary street dust is one of the frequently
encountered practical problems. Additionally, the mentioned trace detection instruments have some drawbacks i.e.
insensitivity to some key compounds, masking by interferents, practical deployment concerns etc. The nature of the
threat from explosives is also increasing by developments in improvised explosive devices (IEDs) which use explosives
manufactured from common domestic chemicals rather than those produced commercially. One example is TATP
(triacetone triperoxide) which was used in the London public transport bombings. Development of sensitive optical
methods to detect these substances with a minimum of sampling effort therefore is a challenge. We will show that
infrared laser spectroscopy in the vapor phase is a powerful method to detect trace amounts of explosives, and is
advantageous to be combined with the established techniques.
In many scenarios standoff-detection would be preferred compared to contact sampling systems. By standoff detection
hidden screening of areas of interest is possible and in case of an alert first measures can be initiated without knowledge
of the suspect. However, no reliable technical solution exists up to now for distances larger than a few m. For
explosives with high vapor pressure infrared laser spectroscopy could be a promising candidate for standoff detection.

2. DETECTION CONCEPTS

2.1 Properties of explosives

The vapor pressures of typical commercial and military explosives and IEDs are shown in Fig.1. These compounds are
often used in combination; for example the commercial explosive SEMTEX is composed of the active ingredients RDX
and PETN along with plasticizers. Some explosives like TATP and EGDN (ethylene glycol dinitrate) have high vapor
pressures even at room temperature which could facilitate vapor phase detection. Detection in the gas phase of other
explosives is not feasible by simple sniffing of the target object. However use of appropriate sampling and desorption
methods could allow particles of the explosive to be captured, concentrated and thermally desorbed to enable the use of
gas phase detection.

*
armin.lambrecht@ipm.fraunhofer.de; phone: +49 761 8857-122; fax + 49 761 8857-224

Quantum Sensing and Nanophotonic Devices VI, edited by Manijeh Razeghi, Rengarajan Sudharsanan, Gail J. Brown,
Proc. of SPIE Vol. 7222, 72220B 2009 SPIE CCC code: 0277-786X/09/$18 doi: 10.1117/12.808976

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 1 in io3 EQN

p-WIT DNtI
I ppm
1 In 1O

00
tUIu) lppb
. ON T

CN
AN TNT
1 in -io9

- I ppi PE TN
1mb ROX

0
I ppq HMX
1 In lu'5
S
0 50 100 150 200 250 300 350
Molecular Weight tamu]

Figure 1: Vapor pressures of typical explosive compounds 10.

Infrared transmission spectroscopy is a analytical tool to detect and identify chemicals in the gas phase. Open path
Fourier transform infrared (FTIR) spectroscopy is an established method to monitor environmental pollutants 1 e.g.
aircraft exhaust gases 2, detect toxic gas emissions at industrial plants 3, and even detect chemical warfare agents
(CWA) 4. Thus open path FTIR is a potential method for explosive detection too. A major drawback of open path FTIR
is the long integration time needed to collect a spectrum because of the low power of the thermal radiation sources
usually employed. This is especially the case if trace compounds have to be detected, which only show up in tiny
spectral features in the spectra.
The basis for detection, sensitivity and selectivity by infrared transmission are the reliable gas phase spectra of the
compounds. Infrared spectra of TATP and TNT in the mid infrared as displayed in Figure 2.

1,2 1,2

1,0
TATP 1,0
TNT

0,8 0,8
absorbance

absorbance

0,6 0,6

0,4 0,4

0,2 0,2

0,0 0,0

-0,2 -0,2
6 7 8 9 6 7 8 9
wavelength / m wavelength / m

Figure 2: Infrared spectra in the gas phase of TATP (left) and TNT (right).The FTIR spectrum of 150 mg/l TATP at 70C shows a
characteristic absorption at 8,35m with a maximum absorbance of 0.38 (left). Infrared spectrum of 90 mg/l TNT at 200C (right).

The sensitivity of infrared spectroscopy is linked to the measurement of small relative transmission changes of e.g. less
than 10-3 at one ore more spectral positions. Selectivity and specificity are linked to the ability to detect differences in
the spectra of two or more species. If spectral features of two compounds overlap at one wavelength, at another
wavelength a difference may occur which could be used to discern between the two species. As is the case with
chemical warfare agents (CWA) for detection of explosives very good sensitivity and a very low false alarm rate i.e.
specificity are a must.5

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 Figure 4: IPM QCL module (left). Basic IPM QCL system for gas detection (middle): QCL driver, detector driver, PC for fast data
acquisition. Open path module (right).

Unfortunately, as can be seen from Figure 2, TATP and TNT like all larger molecules, do not have single line features
in their infrared spectra. The peaks which are shown enlarged in Fig. 5 are much broader than the current tuning range
of a typical QCL of 1 cm-1 to 4 cm-1. Thus scanning across a peak and getting baseline information simultaneously is
not possible by current tuning. For temperature tuning a temperature change of more than 100 K is required. Although
this can be achieved in a rapid way by using a special diamond QCL mounting technique19, the QCL intensity and
emission spectrum are varying with temperature too, which complicates a high resolution signal analysis. We decided to
select QCls with emission at the center of the absorption peaks of TATP resp. TNT (s. Fig. 5). Detection is possible by
just monitoring the transmission signal at this fixed wavelength as a function of time.

0,8 1,2

1,0
TNT
0,6 TATP
0,8
absorbance
absorbance

0,4 0,6

0,4
0,2
0,2
0,0
0,0

-0,2 -0,2
8,0 8,2 8,4 8,6 8,8 9,0 7,0 7,2 7,4 7,6 7,8 8,0
wavelength / m wavelength / m

Figure 5: Absorption bands and QCL emission wavelength. TNT has its prominent absorption band at 7.4 m, TATP at 8.4 m.
The absorption bands have a spectral width > 16 nm. The bars in the graphs show the emission wavelength of the QCLs.

The broad absorption bands may be advantageous, because high power multi mode lasers in pulse operation could be
used. The multimode emission bands cover the main spectral range of the absorption band. In the preferred pulse mode
of operation the manufactures (NanoPlus GmbH, Alpes Laser, Fraunhofer IAF) offer devices with an average power of
more than several milliwatts with sub amp threshold currents. On the other hand with multimode lasers noise
characteristics and spectral interferences have to be considered carefully (e.g. with the water absorption line in Fig. 3).
The sensitivity depends on the stability and noise of the laser emission intensity. We first like to focus on the sensitivity
issue- i.e. the amount of explosive material we can detect in a specific experimental configuration in the lab. A next step
will be the issue of the selectivity. In this case we are going to use a second laser wavelength as a reference channel.

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 Figure 4: IPM QCL module (left). Basic IPM QCL system for gas detection (middle): QCL driver, detector driver, PC for fast data
acquisition. Open path module (right).

Unfortunately, as can be seen from Figure 2, TATP and TNT like all larger molecules, do not have single line features
in their infrared spectra. The peaks which are shown enlarged in Fig. 5 are much broader than the current tuning range
of a typical QCL of 1 cm-1 to 4 cm-1. Thus scanning across a peak and getting baseline information simultaneously is
not possible by current tuning. For temperature tuning a temperature change of more than 100 K is required. Although
this can be achieved in a rapid way by using a special diamond QCL mounting technique19, the QCL intensity and
emission spectrum are varying with temperature too, which complicates a high resolution signal analysis. We decided to
select QCls with emission at the center of the absorption peaks of TATP resp. TNT (s. Fig. 5). Detection is possible by
just monitoring the transmission signal at this fixed wavelength as a function of time.

0,8 1,2

1,0
TNT
0,6 TATP
0,8
absorbance
absorbance

0,4 0,6

0,4
0,2
0,2
0,0
0,0

-0,2 -0,2
8,0 8,2 8,4 8,6 8,8 9,0 7,0 7,2 7,4 7,6 7,8 8,0
wavelength / m wavelength / m

Figure 5: Absorption bands and QCL emission wavelength. TNT has its prominent absorption band at 7.4 m, TATP at 8.4 m.
The absorption bands have a spectral width > 16 nm. The bars in the graphs show the emission wavelength of the QCLs.

The broad absorption bands may be advantageous, because high power multi mode lasers in pulse operation could be
used. The multimode emission bands cover the main spectral range of the absorption band. In the preferred pulse mode
of operation the manufactures (NanoPlus GmbH, Alpes Laser, Fraunhofer IAF) offer devices with an average power of
more than several milliwatts with sub amp threshold currents. On the other hand with multimode lasers noise
characteristics and spectral interferences have to be considered carefully (e.g. with the water absorption line in Fig. 3).
The sensitivity depends on the stability and noise of the laser emission intensity. We first like to focus on the sensitivity
issue- i.e. the amount of explosive material we can detect in a specific experimental configuration in the lab. A next step
will be the issue of the selectivity. In this case we are going to use a second laser wavelength as a reference channel.

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 Ideally, the reference wavelength signal should not be affected by the explosive material but by all other background
materials possibly present. The two channel concept is quite common, e.g. in non dispersive infrared (NDIR) sensors.
Figure 3 illustrates the situation for TATP: the sample wavelength at 8.4 m has to be carefully chosen not to coincide
with a water absorption line. The interference of ethanol could be compensated by a reference channel at 8.0m or
9.0m.
The spectroscopic situation is very similar to the detection of glucose in aqueous solutions by QCL spectroscopy 20,
where for continuous diabetes control high sensitivity and specificity is required. Here transmission sensitivity below
10-3 was achieved, depending on the noise characteristics of the setup.
Recently broadly tunable external cavity QCL became commercially available (Daylight Solutions, Inc., Poway, CA,
USA). Fast continuous tuning across more than 100 cm-1 with high photometric stability of the laser emission could be a
a new and favorable solution for broad absorbers.

2.3 Standoff detection

The basic concept of a QCL open path setup for explosive detection is shown in Fig. 6. It consists basically of QCL and
detector modules with long distance optics on a tripod, and a cornercube reflector. To cope with cross sensitivities a
setup with two QCL modules for sensing and reference wavelengths will be employed. In a realistic scenario, the plume
of the evaporating explosive material e.g. TATP is diluted and disturbed by movements and air flow. The material could
be encapsulated or hidden below clothing, or only traces are left on the surface. Thus gas phase concentration probably
will we much lower than the equilibrium values in figure 1. Hence we first have to determine our detection limits with
well defined samples and conditions in the laboratory. This is described in sections 3.1 and 4.1.

"Open Path" Unit: emission and

detection module

TATP-
Plume Corner Cube
Control Unit Mirror

Figure 6: Basic concept of open path setup for explosive detection.

2.4 Extractive optical detection for contactless sampling:

With extractive detection of samples the sampling is the most critical part of the system. Usually samples are collected
by wiping or by collection of dust from air flows similar to a vacuum cleaner. For an efficient explosive detection this
has to be done in a short time, and contamination and dilution of the sample have to be avoided. We consider material
which is sampled in the solid phase but could be desorbed or evaporated into the gas phase where specific detection
takes place. By appropriate sampling and desorption mechanisms, preselection and preconcentration could be
performed. For example by electrostatic filtering only certain particle may be sampled; by well defined heating /
temperature control during desorption a further selection is feasible. Optical detection can be a powerful addition to
other methods like IMS and GC-MS to overcome their limitations and enhance sensitivity and selectivity. Additionally,
optical methods can be used continuously, and may serve as fast screening stages prior to e.g. GC-MS.
For transmission spectroscopy a very small volume of the sample cell and a long optical path length is needed to
achieve a high sensitivity, and several solutions are described in the literature 21, 22. For explosive detection we will show
that hollow fibers 23 form the ideal cell to cope with small volumes of sample gas and to avoid further dilution. These

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 waveguides unlike common optical fibers have an air core where the radiation is guided by reflection at a mirror
layer that covers the inner side of the fiber-cladding. At the same time a gas can flow through the air core and absorb the
infrared radiation specifically. Since the core diameters of these fibers are in the range of 300 to 1000 m a long optical
path can be obtained for a small gas volume. Such fibers are commercially available at Polymicro, Inc.
The basic concept of our extractive optical detection setup is shown in Fig. 7. The collected material is on a suitable
carrier is heated in special desorption unit to transfer the sample into the gas phase. By a carrier gas the sample gas is
introduced into a heated hollow fiber which serves simultaneously as an optical waveguide for the radiation of a QCL.
By laser transmission spectroscopy the volume in the cell is probed and the explosive material is detected. Details of the
experimental configuration will be described in the following.

Lamp Purge or pump

membrane
Desorption
Ref. unit
Signal
QCLaser + TEC +
Current supply
Heated Hollow fiber
MCT / pyro
detector
QCL control: pulse
mode / temp.
Lock in amplifier /
Oscilloscope

Figure 7: System concept for extractive detection

3. EXPERIMENTAL

3.1 TATP and TNT samples

For TATP experiments samples were provided by the Fraunhofer ICT in the framework of the Fraunhofer project
OFDEX. To ensure safe transport and handling of small amounts of explosive material a few mg of TATP are
hermetically enclosed in aluminum cans which normally are used in differential scanning calorimetry (DSC). These
cans have a diameter of approximately 5mm. The cans are opened by just piercing them with a needle and TATP starts
to evaporate. The opened cans can be placed onto a heater or into a heated container.
For the TNT experiments performed with the extractive setup two types of samples were used. Usually we used a
mixture of 20 %TNT and 80% SiO2-sand, supplied by Fraunhofer ICT. Later first experiments were performed with
samples collected onto membranes from automatic trace sampling supplied by the Ray Detection Technologies, Inc. (s.
Fig. 8). These samples consist of real dust background spiked with TNT traces.

Figure 8: TATP and TNT samples: TATP is hermetical enclosed in an aluminum metal can (right) of 5mm diameter (right). TNT is
collected on sampling membranes together with real dust background. The membrane (actual size approximately 3 cm diameter)
contains TNT particulate and vapor residues (left).

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 3.2. TATP open path detection
Two setups to perform laboratory experiments with well defined TATP samples are shown in Figure 9.
The collimated beam of a QCL passes through a heated open glass tube. Inside the tube a TATP sample was placed
onto a extra small heater. When the heater is switched on, TATP evaporated inside the open tube. Condensation on the
walls is prevented by heating the tube walls. The tube can be easily rinsed by air flow to recover the baseline signal.
Compared to closed cells no uniform gas concentrations values are obtained. However, this setup is more realistic and
window effects are avoided. To prevent laser light bypassing the rather small tube the laser passes an aperture of 10 mm
diameter, and the tube was shielded by a piece of paper in Fig. 9 (left). In contrast to previous measurements with our
QCL system using short pulses, we were able to use QCL from Fraunhofer-IAF for TATP which can stand long pulses
up to 100 s with a repetition rate of 500 kHz. This operation mode enables the use of a pyroelectric detector instead of
the fast HgCdTe (MCT) detectors previously employed. Despite the lower sensitivity of the detectors the signal is more
linear and stable, and a lock-in technique can be used.
To study interferences by other atmospheric constituents, a two channel setup was recently assembled, which consists
of two QCL modules with sample and reference wavelengths (s. Fig. 9 right). In this case a closed cell is employed
which could be positioned before or behind the open cell for the explosive sample. A chopper is used to switch between
measurement and a reference path, to monitor the intensities of the two laser sources. Only one pyroelectric detector is
used in this case to avoid possible drift effects due to two independent detectors. This configuration is similar to the one
previously described 20. First experiments with the two channel setup on cross sensitivities with e. g. ethanol and water
vapor confirm the expectations of chapter 2. Further details will be published elsewhere 24.

detector

open tube

optical path
aperture
QCL-module

Figure 9: Laboratory setup with heated open tube (left). Laboratory setup with two QCL modules for two wavelengths
measurements with reference and measurement paths (right).

3.3 TATP and TNT hollow fiber detection

For hollow fiber gas detection the setup shown in Fig. 10 is used. It consists of a sample chamber, where a small
amount of TATP or TNT is heated, and almost equilibrium vapor pressure values are obtained. By slightly pressurizing
with N2 part of the chamber gas is introduced into the hollow fiber. The hollow fiber can be heated to approximately
90C to prevent condensation at the fiber walls.
For TATP the sample cans (s. Fig. 8) were pierced open and immediately introduced into the desorption chamber. For
TNT weighed samples with a mass of a few mg (from a mixture of TNT and sand) were introduced into the desorption
chamber.
As mentioned above, hollow fibers can provide very small sample volumes. For comparison, the 10 cm cell used for the
measurement in Fig. 2 has a volume of 57 ml which requires 5 mg TATP for saturation with a vapor pressure 1400 Pa
at 70C. In our system setup a 50 cm long fiber with 750 m hollow core is used. This means that the gas cell has a
volume of only 0.22 ml. The light of the QCL is focused into the fiber by a mirror objective with 140 mm focal length.
A beam splitter reflects 10% on a reference detector for monitoring the laser intensity. The fiber ends and the adapters

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 have standard FC coupling. The adapters are fixed in a cylindrical mount with laser window and tight gas channel. The
volume of the two hollow parts in the adapters, the sampler chamber volume, connecting capillary tubes, and the fittings
are added to the fiber core volume (0.22 ml), resulting in a total volume of around 10 ml. At the other end of the hollow
fiber the IR light is focused onto the signal detector.

Figure 10: Setup showing desorption cell with heating elements and power supply (left), QCL module and collimation optics (top),
beam splitter (middle), reference detector (right), and hollow fiber in heating hose (bottom). The desorption cell is shown in the right
figure. A lamp heats up the sample and the explosive is evaporated. In order to avoid condensation the body of the unit is heated up
to 100C. A nitrogen purge transfers the gas into the fiber.

Depending on the laser specifications two different measurement modes were used for TATP and TNT.
The TATP measurements were done with short pulses. The QCL pulse width was 100 ns and the repetition rate was 50
kHz, so a duty cycle of 0.5% was achieved. In this operation mode the laser emits up to 30 mW. A fast TE cooled mid
IR detector (Vigo Ltd.) is necessary for the fast pulses. A 200 MHz oscilloscope records and averages the transients and
is read out by a computer. For the TNT measurements the QCL operates with much longer pulses of 10 s at 700 Hz
repetition rate. Because of the long pulses a pyrodetector (Infratec LME353) and a digital lock in amplifier (Perkin
Elmer) can be used.
In both cases the noise equivalent limit of relative transmission changes was approximately 0.15%.. Short pulses work
with most of the QCLs because the thermal load on the QCL chip is lower. Due to the continuous progress of QCL
development during the last years most new QCLs can operate with long pulses up to cw.

4. RESULTS AND DISCUSSION

4.1 open path detection
The changes in the optical transmission expected for detection of TATP vapor are very small. Thus an excellent
stability of the laser power and very low noise of the whole signal chain are necessary. By using a single mode DFB
laser from Fraunhofer- IAF emitting at 1200 cm-1 operating with 100s pulses at a duty cycle of 5% a reasonable
stability and noise of the output power was achieved (s. Fig. 11). A relative standard deviation of 1.2 * 10-3 over 5 min
was obtained. The maximum spikes in Fig. 11 amount to 5 * 10-3.

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 1,490 1,175
(1) (2) together < 50g
DFB QCL: 9,5 V; 260 K; 100s; 500Hz
100g 70g (3) (4)

detector signal / mV
DC 5% 1,150
1,485
amplitude / mV

1,125
1,480

2.
1,100

5p
pm
5.
2p
7. pp
1,475

*m
6p m
12

pm
-3 1,075

.1

pm *m
relative standard deviation: 1,2*10

*m
*m
1,470
0 100 200 300 1,050
800 1200 1600
time / s time / s

Figure 11: Laser stability of the QCL-Laser (left) and TATP measurement results using open cell (right).

The result of a TATP measurement with the open cell and a time interval of 10 min is shown in Fig. 11 (right). The
TATP grains in the sample holder evaporate subsequently in separate gas bursts. By using spectroscopic data these
bursts can be approximately correlated with a certain material mass which is indicated in Fig. 11. Th first two bursts
correspond to some 100g material which can be translated to a columnar concentration of 12.1 ppm*m (for a
hypothetically 1 m long cell). These first bursts induce a relative signal change of some 4%. The smallest peaks
observed correspond to 2.5 ppm*m. After evaporation of all TATP grains the initial signal level was recovered.
As a result open path measurements of TATP columnar concentrations in the 5 ppm*m range are feasible in a
laboratory situation. The special dynamics of the TATP evaporation can be observed with fast instruments and may
serve as additional information for the detection of the material. In the next step cross sensitivities have to be
investigated. However, for realistic standoff- scenarios the expected TATP vapour phase concentrations are often much
lower than the currently achieved sensitivity limits of our setup.

4.2 hollow fiber detection

For TATP detection an 8.2m-QCL (from Alpes Lasers, SA) was operated with short pulses, thus fast MCT detector
and data acquisition with the oscilloscope were needed.
The measurement shown in Fig. 12 (left) was done without heating the fiber. The vapor pressure of TATP is sufficient
high to have significant TATP gas concentrations at room temperature. To obtain a fast signal change the heating of the
desorption unit to 90C was used to evaporate the 1.5 mg TATP sample in a minute. But due to the cold fiber the
equilibrium vapor pressure in the fiber corresponds to a temperature of around 23C. The disadvantage of this method is
that recovering of the signal takes several hours to evaporate and remove completely the condensed TATP from the
fiber walls.
The result of the TATP measurement is shown in Figure 12 (left). At 90C the saturation vapor pressure of TATP is 110
hPa.25 Thus in the desorption chamber a maximum TATP volume concentration of 11 % is reached. With a fiber length
of 50 cm roughly a 50% transmission change is obtained. The fiber has room temperature (23C), so the saturation
vapor pressure is around 4.3 Pa. For an estimation of the detection limit we assume that in the fiber a vapour phase
concentration of 43 ppm TATP is obtained. The analysis of the noise without TATP signal shows that a transmission
change of 0.5% (~3) is detectable for such an instrument, i.e. a concentration of 0.43 ppm. Thus, taking only a
sensitive fiber volume of 0.2 ml (neglecting dead volumes of fittings etc.), an estimate of the TATP density in the gas
phase of 10g/l, this translates to a detection limit of < 1 ng.
Because dead volumes always will be present, a realistic detection limit is estimated to be 10-100 times higher.
However, by using micromachined components to reduce dead volumes a much lower detection limit is feasible.

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 1,0 baseline at 90 C heating temperature input, heating off
pressure on
IA I Into desorption device
1,0 -
0,9 and flux on

0 0,9 -
0,8
outgasslng of TATP into hollow fiber
E 0,8 -
heating on again additional
pressure
0,7 -

saturation 0,6 -

u,o 0,5 - vapor pressure increasing by increasing temperature -

0 1000 2000 3000 4000 5000 6000 7000
500 1000 1500 2000 2500 3000
time I S time / S

Figure 12: QCL based infrared transmission measurement of 1.5 mg TATP introduced into desorption stage and vapor extraction
through hollow fiber cell (left). QCL detection of 2mg TNT using the same method (right).

The TNT measurements were done with a QCL emitting at 7.4m supplied by Nanoplus GmbH. As mentioned above
long pulses, pyrodetectors, and lock-in detection scheme were used.
For the experiments a fiber heating jacket was installed to prevent condensation of the TNT at the fiber walls, keeping
the fiber at 90C. The 10 mg TNT sand (20% TNT+80% sand) sample shows a 40% transmission change. The spikes
on the measurement are caused by electric disturbances due to the heating control of the desorption unit. Heating was
switched off at 300 s in order to have a less noisy signal. Heating was switched on again at 750 s. After 2000 s the
transmission signal recovers, this shows that the TNT did not condensate in the fiber.
The estimation of the TNT detection limit is similar to that of TATP. The sample contains 2 mg TNT (the rest is sand).
The vapor pressure of 10 Pa corresponds to 100 ppm and this to 741 mg/m (molecular weight of TNT is 227 g/mol).
This means that 7.41 g TNT gas is in the chamber volume of 10 ml, if the saturation is achieved. Correspondingly, in
the fiber alone (0.2 ml) 148 ng TNT are present. The spectrometer can resolve a transmission change of 0.5% (3). So
the detection limit for TNT gas at 90Cin the fiber is around 2 ng.
As with TATP dead volumes always will be present, thus a realistic detection limit is estimated to be 10-100 times
higher.
First experiments with eight membranes from the automated trace sampling with real contamination background were
performed. Four membranes had no or only a low TNT contamination which could not detected. The other four samples
showed a significant transmission change by 4 %. The calculation yields a total TNT contamination of some 600 ng.
Further details are published elsewhere.24

5. CONCLUSION AND OUTLOOK

The feasibility of standoff and extractive vapor phase explosive detection of TATP and TNT with mid infrared QCL
spectroscopy was investigated. A detection limit of 5 ppm*m for TATP was achieved for open path detection in the
laboratory. Due to the broad spectral signatures of TATP and TNT scanning across the characteristic absorption lines by
tuning of a single laser was not possible. Thus the detection limit is determined by the intensity noise and drift stability
of the QCL. We obtained a relative standard deviation of 1.2 * 10-3 over 5 min, depending on laser properties and
operation parameters. To increase specificity a second reference laser will be used. In a later stage selectivity can be
achieved by using broadly tunable external cavity QCL which recently became commercially available (Daylight
Solutions, Inc., Poway, CA, USA).

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 For long distance standoff scenarios the TATP vapour phase concentrations probably are much lower than the currently
obtained detection limits of our setup. However by appropriate beam folding e.g. in an optical portal configuration
much higher sensitivities can be expected.
If only very small sample amounts are available, which is the case for extractive trace explosive detection, hollow fibers
offer a promising solution. TATP and TNT vapor phase detection was demonstrated with a hollow fiber QCL setup.
Detection of a few ng of explosive material within a few seconds is feasible because of the small volume of the hollow
fibers. However, dead volumes (desorption chamber, connecting capillaries, fittings, adapters for gas and light coupling
at the fiber ends) limit the sensitivity. Summing up to approximately 10 ml in our setup the detection limit was in the
100 ng range.
This situation is similar to (micro-) GC development, where minimization of volumes is essential, too. By micro-
fabrication technology we expect the dead volumes to be reduced below 1 ml, i.e. to the same range as the fiber volume.
A promising concept is the complete integration of a rigid hollow waveguide with connecting micro gas fluidic
components into a solid device, e.g. a silicon chip. This would enable ng optical detection and could be hyphenated with
other miniaturized analyzers like GC or IMS.

ACKNOWLEDGEMENTS

Support by the European community within the NoE GOSPEL and by the Fraunhofer internal programs (MaVo
OFDEX) is gratefully acknowledged. We like to mention our partners from Fraunhofer ICT for supply of explosive
samples and Fraunhofer IAF for QCL devices. Special thanks to Ms. W. Schweikert from Fraunhofer ICT for her help
with the infrared spectra.
We also like to thank Nanoplus GmbH for their QCLs. Special thanks to G. Mller (EADS, Ottobrunn, Germany) for
providing the desorption device and to S. Bchler (Ray Detection Technologies, Holon, Israel) for the sampling
membranes.

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