We present initial results on the performance of a compressive sensing setup for Raman imaging spectroscopy for standoff trace explosives detection. Hyperspectral image reconstruction is demonstrated under low signal conditions and successful spatial separation of substances with close lying Raman peaks is shown.
Imaging Raman spectroscopy based on tunable filters is an established technique for detecting single explosives particles
at stand-off distances. However, large light losses are inherent in the design due to sequential imaging at different
wavelengths, leading to effective transmission often well below 1 %.
The use of digital micromirror devices (DMD) and compressive sensing (CS) in imaging Raman explosives trace
detection can improve light throughput and add significant flexibility compared to existing systems. DMDs are based on
mature microelectronics technology, and are compact, scalable, and can be customized for specific tasks, including new
functions not available with current technologies.
This paper has been focusing on investigating how a DMD can be used when applying CS-based imaging Raman
spectroscopy on stand-off explosives trace detection, and evaluating the performance in terms of light throughput, image
reconstruction ability and potential detection limits. This type of setup also gives the possibility to combine imaging
Raman with non-spatially resolved fluorescence suppression techniques, such as Kerr gating.
The system used consists of a 2nd harmonics Nd:YAG laser for sample excitation, collection optics, DMD, CMOScamera
and a spectrometer with ICCD camera for signal gating and detection.
Initial results for compressive sensing imaging Raman shows a stable reconstruction procedure even at low signals and
in presence of interfering background signal. It is also shown to give increased effective light transmission without
sacrificing molecular specificity or area coverage compared to filter based imaging Raman. At the same time it adds
flexibility so the setup can be customized for new functionality.
We present preliminary results on the performance of a basic stand-off Raman spectroscopy setup using coded apertures compared to a setup using a round-to-slit fiber for light collection. Measurements were performed using single 5 ns laser shots at 355 nm with a target distance of 5.4 meters on ammonium nitrate powder. The results show an increase in signal-to-noise ratio of 3-8 times when using coded aperture multiplexing compared to the fiber setup.
The following paper presents a realistic forensic capability test of an imaging Raman spectroscopy based demonstrator system, developed at FOI, the Swedish Defence Research Agency. The system uses a 532 nm laser to irradiate a surface of 25×25mm. The backscattered radiation from the surface is collected by an 8” telescope with subsequent optical system, and is finally imaged onto an ICCD camera. We present here an explosives trace analysis study of samples collected from a realistic scenario after a detonation. A left-behind 5 kg IED, based on ammonium nitrate with a TNT (2,4,6-trinitrotoluene) booster, was detonated in a plastic garbage bin. Aluminum sample plates were mounted vertically on a holder approximately 6 m from the point of detonation. Minutes after the detonation, the samples were analyzed with stand-off imaging Raman spectroscopy from a distance of 10 m. Trace amounts could be detected from the secondary explosive (ammonium nitrate with an analysis time of 1 min. Measurement results also indicated detection of residues from the booster (TNT). The sample plates were subsequently swabbed and analyzed with HPLC and GC-MS analyses to confirm the results from the stand-off imaging Raman system. The presented findings indicate that it is possible to determine the type of explosive used in an IED from a distance, within minutes after the attack, and without tampering with physical evidence at the crime scene.
Standoff Raman imaging systems have shown the ability to detect single explosives particles. However, in many cases, the laser intensities needed restrict the applications where they can be safely used. A new generation imaging Raman system has been developed based on a 355 nm UV laser that, in addition to eye safety, allows discrete and invisible measurements. Non-dangerous exposure levels for the eye are several orders of magnitude higher in UVA than in the visible range that previously has been used. The UV Raman system has been built based on an UV Fabry-Perot Interferometer (UV-FPI) developed by VTT. The design allows for precise selection of Raman shifts in combination with high out-of-band blocking. The stable operation of the UV-FPI module under varying environmental conditions is arranged by controlling the temperature of the module and using a closed loop control of the FPI air gap based on capacitive measurement. The system presented consists of a 3rd harmonics Nd:YAG laser with 1.5 W average output at 1000 Hz, a 200 mm Schmidt-Cassegrain telescope, UV-FPI filter and an ICCD camera for signal gating and detection. The design principal leads to a Raman spectrum in each image pixel. The system is designed for field use and easy manoeuvring. Preliminary results show that in measurements of <60 s on 10 m distance, single AN particles of <300 μm diameter can be identified.
A stand-off Raman imaging system for the identification of explosive traces was modified for the analysis of substances in containers which are non-transparent to the human eye. This extends its application from trace detection of threat materials to the investigation of suspicious container content. Despite its limitation to containers that are opaque to the facilitated laser, the combination of Spatial Offset Raman Spectroscopy (SORS) with stand-off Raman imaging allows to collect spectral data from a broad range of different spatial offsets simultaneously. This is a significant advantage over SORS with predefined offset, since the ideal offset is unknown prior to the measurement and depends on the container material as well as the sample content. Here the detection of sodium chlorate in a white plastic bottle is shown. A 532nm-laser (pulse length 5ns, repetition 50kHz) was focused to a diameter of 10mm at 10m. A 1500mm Schmidt-Cassegrain telescope with a 152.4mm diameter collected the scattered light. An edge filter removed inelastically scattered laser light and a liquid crystal tunable filter was used to select 0.25nm broad wavelength ranges between 480 and 720nm. The sample area of 50×50mm was imaged on 1024×1024 pixels of an ICCD camera. For the conducted experiments an ICCD gate time of 5ns was selected and 70μJ-laser pulses were accumulated during 1s for each wavelength.
This paper describes a system for stand-off vapor detection based on Resonant Raman spectroscopy, RRS. The system is a step towards a RRS LIDAR (Light Detection And Ranging) system, capable of detecting vapors from explosives and explosives precursors at long distances. The current system was used to detect the vapor of nitromethane and mononitrotoluene outdoors in the open air, at a stand-off distance of 11–13 meters. Also, the signal dependence upon irradiation wavelength and sample concentration was studied in controlled laboratory conditions. A tunable Optical Parametric Oscillator pumped by an Nd:YAG laser, with a pulse length of 6 ns, was operated in the UV range of interest, 210–400 nm, illuminating the sample vapor. The backscattered Raman signal was collected by a telescope and a roundto- slit optical fiber was used to transmit collected light to the spectrometer with minimum losses. A gated intensified charge-coupled device (ICCD) registered the spectra. The nitromethane cross section was resonance enhanced more than a factor 30 700, when measured at 220 nm, compared to the 532 nm value. The results show that a decrease in concentration can have a positive effect on the sensitivity of the system, due to a decrease in absorption and selfabsorption in the sample.
This paper describes how optical Kerr gating can be used for effective rejection of fluorescence from Raman spectra of explosives and explosives precursors. Several explosives are highly fluorescent, and this method enables Raman detection of explosives materials that would else be complicated or impossible to identify. Where electronic cameras (intensified charge-coupled devices, ICCDs) have showed not yet to be sufficiently fast to be used for rejection of this fluorescence, Kerr gating is here proved to be an efficient alternative, demonstrated by measurements on plastic explosives. Results were obtained using a gating time of ~30 ps. The Kerr gate was driven by the fundamental mode of an Nd:YAG laser, at 1064 nm, with pulses of ~8 mJ, 50 Hz and 30 ps. CS2 was used as a Kerr medium and Glan polarizing prisms were important features of the system. Raman spectra were obtained using a 532 nm probe wavelength, from the same Nd:YAG laser being frequency doubled, with a ~2 mJ pulse energy. Gating times of ~30 ps were thus achieved, with a fluorescence rejection factor of more than 1300, for the first time revealing detailed characteristics in Raman spectra from highly fluorescent PETN based plastic explosive.
At the Swedish Defence Research Agency, FOI, Raman spectroscopy is used to detect explosives at stand-off distances. A technique based on imaging Raman spectroscopy has been shown to have the potential to detect trace amounts of explosives at stand-off distances. In this publication we provide limits of detection with the current imaging Raman setup for four different substances, cyclotrimethylenetrinitramine (RDX), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and sulfur. The limits of detection for DNT and TNT were found to be about 0,5 μg while the lowest limit of detection was achieved for sulfur at 200 ng. The detection limit for RDX is 25,9 μg.
Multispectral imaging Raman spectroscopy is a novel technique for detecting and identifying explosive residues, e.g.
explosives particles which are left on surfaces after handling or manufacturing of explosives.
By imaging a suspect surface using the imaging Raman technique, explosives particles at stand-off distances can be
identified and displayed using color coding1.
In this paper we present an attempt to determine a limit of detection for imaging Raman spectroscopy by analyzing holes
of various sizes in aluminum plates filled with four different substances; 2,4-dinitrotoulene (DNT), ammonium nitrate
(AN), sulfur, and 2,4,6-trinitrotoulene (TNT). The detection time in the presented experiments has not been optimized,
instead more effort has been invested in order to reduce false alarms. The detection system used is equipped with a green
second harmonic Nd:YAG laser with an average power of 2 W, a 200 mm telescope and a liquid crystal tunable filter to
scan the wavenumbers. The distance to the target was 10 m and the imaged area was 28 mm × 28 mm. The measured
multi-spectral data cubes were evaluated using least square fitting to distinguish between DNT, AN,S, TNT and the
background. The detection limit has been determined to be sub microgram using the current setup.
This paper presents the ongoing development of a laser ionization mass spectrometric system to be applied for screening
for security related threat substances, specifically explosives. The system will be part of a larger security checkpoint
system developed and demonstrated within the FP7 project EFFISEC to aid border police and customs at outer border
checks. The laser ionization method of choice is SPI (single photon ionization), but the system also incorporates optional
functionalities such as a cold trap and/or a particle concentrator to facilitate detection of minute amounts of explosives.
The possibility of using jet-REMPI as a verification means is being scrutinized. Automated functionality and user
friendliness is also considered in the demo system development.
This paper provides a brief overview of the Raman-based standoff detection methods developed at FOI for the purpose
of standoff explosives detection. The methods concerned are Raman imaging for particle detection and Resonance
Enhanced Raman Spectroscopy for vapor detection. These methods are today reaching a maturity level that makes it
possible to consider applications such as trace residue field measurements, on site post blast analysis and other security
of explosives related applications.
The paper will look into future possible applications of these technologies. Our group has extensive activities in
applications of the technology, among others in projects for the Seventh Framework Program of the European Union.
Some of these possible applications will be described and a look into future development needs will be made.
As far as possible, applicability will be discussed with a view on realistic explosives trace availability for detection.
Necessary data to make such realistic applicability assessment is not always available and a brief discussion on the
applicability of using the developed Raman technology to obtain this kind of data will also be made. The aspects of
transitioning from research to practical applications, considering also eye-safety of the system, will be discussed as well.
Helena Hansson, Anders Elfving, Dennis Menning, Hans Önnerud, Erik Holmgren, Mona Brantlind, Ulla Hedebrant, Henric Östmark, Rose-Marie Karlsson, Patrick Goede
The main objective of this project is to study the difference between aged and un-aged post-blast residues and nonblasted
explosives.
Sand from the post-blast scenes was subjected to accelerated aging (temperature, light and addition of water) over a
period of 20 weeks. The samples were aged as matrix-free pure compounds and as post-blast sand. Several explosive
materials were detonated over sand-filled containers and selected residues were separated and detected with HPLC/UV.
Separation and detection methods using GC/MS and LC/UV were developed.
This screening study of aged post-blast residues revealed that most of the residues reached low or undetectable
concentration within a period of eight weeks of aging. This degradation rate theory can be applied both for the
temperature- and UV-aged samples. The half-life degradation time (t1/2) was estimated and most of the detected residues
reach t1/2 within five weeks. No trends with significant difference can be seen between the UV- and temperature-aged
samples.
Results of dispersion experiments and dispersion modelling of explosives, drugs, and their precursors will be presented.
The dispersion of chemicals evolving during preparation of home made explosives and a drug produced in an improvised
manner in an ordinary kitchen has been measured. Experiments with concentration of hydrogen peroxide have been
performed during spring and summer of 2009 and 2010 and further experiments with concentration of hydrogen
peroxide, synthesis and drying of TATP and Methamphetamine are planned for the spring and summer of 2011.
Results from the experiments are compared to dispersion modelling to achieve a better understanding of the dispersion
processes and the resulting substances and amounts available for detection outside the kitchen at distances of 10-30 m
and longer. Typical concentration levels have been determined as a function of environmental conditions.
The experiments and modelling are made as a part of the LOTUS project aimed at detecting and locating the illicit
production of explosives and drugs in an urban environment. It can be concluded that the proposed LOTUS system
concept, using mobile automatic sensors, data transfer, location via GSM/GPS for on-line detection of illicit production
of explosive or precursors to explosives and drugs is a viable approach and is in accordance with historical and today's
illicit bomb manufacturing.
The overall objective and approach of the LOTUS project will also be presented together with two more projects called
PREVAIL and EMPHASIS both aiming at hindering or finding illicit production of home made explosives.
A multispectral imaging technique has been developed to detect and identify explosive particles, e.g. from a fingerprint,
at stand-off distances using Raman spectroscopy.
When handling IED's as well as other explosive devices, residues can easily be transferred via fingerprints onto other
surfaces e.g. car handles, gear sticks and suite cases. By imaging the surface using multispectral imaging Raman
technique the explosive particles can be identified and displayed using color-coding.
The technique has been demonstrated by detecting fingerprints containing significant amounts of 2,4-dinitrotoulene
(DNT), 2,4,6-trinitrotoulene (TNT) and ammonium nitrate at a distance of 12 m in less than 90 seconds
(22 images × 4 seconds)1. For each measurement, a sequence of images, one image for each wave number, is recorded.
The spectral data from each pixel is compared with reference spectra of the substances to be detected. The pixels are
marked with different colors corresponding to the detected substances in the fingerprint.
The system has now been further developed to become less complex and thereby less sensitive to the environment such
as temperature fluctuations. The optical resolution has been improved to less than 70 μm measured at 546 nm
wavelength. The total detection time is ranging from less then one minute to around five minutes depending on the size
of the particles and how confident the identification should be. The results indicate a great potential for multi-spectral
imaging Raman spectroscopy as a stand-off technique for detection of single explosive particles.
Portendo has in collaboration with FOI, the Swedish Defence Research Agency, developed a world-leading
technique of trace detection of explosives at standoff distance using Raman spectroscopy. The technology is
further developed in order to enhance the sensitivity of the method and to be able to extend the field of
applications. Raman scattering is a well-established technique able to detect substances down to single
micrograms at standoff distances, however, one of the obstacles limiting the detection possibilities is interfering
fluorescence, originating either from the substance itself or from the surrounding material. One main challenge
for this technology is thus to either omit the excitation of the fluorescent process altogether or to be able to
separate the two processes and only detect the Raman signal.
Due to the difference in the temporal behavior of the two processes - Raman scattering occurs in the order of
femtoseconds while fluorescence typically has a lifetime in the order of nanoseconds - one way to theoretically
separate them is to limit the measurement to as short time as possible, cutting off most of the emitted
fluorescence. The improvement depends on how much of the fluorescence can be omitted without decreasing
the Raman signal. Experimentally, we have verified this improvement in signal to noise ratio when using a laser
with picosecond pulses instead of nanosecond pulses, which has resulted in an improvement in SNR of up to 7
times for bulk ANFO. These results verify the predicted signal enhancement and suggest higher sensitivity for
standoff detection in future systems.
Stand-off measurements on nitromethane (NM), 2,4-DNT and 2,4,6-TNT in vapor phase using resonance Raman
spectroscopy have been performed. The Raman cross sections for NM, DNT and TNT in vapor phase have been
measured in the wavelength range 210-300 nm under laboratory conditions, in order to estimate how large resonance
enhancement factors can be achieved for these explosives. The measurements show that the signal is greatly enhanced,
up to 250.000 times for 2,4-DNT and 60.000 times for 2,4,6-TNT compared to the non-resonant signal at 532 nm. For
NM the resonance enhancement enabled realistic outdoor measurements in vapor phase at 13 m distance. This all
indicate a potential for resonance Raman spectroscopy as a stand-off technique for detection of vapor phase explosives.
This paper gives a brief overview on our latest progress in the area of standoff detection. Standoff Raman measurements
from 200 m and 470 m distance have been performed on bulk amounts of TATP and AN respectively, the former
through a double sided window, the latter under heavy rain. Resonance Raman measurements on TNT, DNT and NM
vapors in the ppm concentration regime are presented, showing resonance enhancement in the range of 2 200 (NM) to
57 000 (TNT) as compared to 532 nm Raman cross sections. Finally, the application of hyper spectral Raman imaging is
described, exemplified by the resolution of four different samples (sulphur, AN, DNT, and TNT) in the form of 5 mm
wide discs in one single image.
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