"Vapor and Trace Detection of Explosives for Anti-Terrorism Purposes"

The September 11th disaster was a global wake-up-call about the danger of terrorism. This event initiates different preventive and active measures against this threat. In the field of Landmine-detection several detection techniques have been developed and International workshops has been organized in the past to exchange experiences in this field, also some "Advanced Research Workshops" of the NATO Science Program was hold in the past years (Moscow, Prague, St. Petersburg). Some aspects of the explosives detection in the case of terrorism correspond to the detection of landmine detection, e.g. small vapor concentrations, variable surroundings, therefore experiences in land-mine detection seemed to be helpful in this discussion. Moreover a very wide area of different methods and techniques were investigated in this field. On the other hand there are a lot of differences between both areas of explosive detection: other explosive materials, shorter time of detection, different locations and placing, different volumes inhomogeneous surroundings, different confinements, explosive charges as distributor for chemical, nuclear or biological agents. etc.. Because of the complexity of explosives detection and obliged to the wish for more effort in explosives detection the interdisciplinary discussion of scientists seemed to be important. It is the aim of this proposed ARW to provide an opportunity for researchers from east and west to share their experiences, approaches in there research work and considerations for future investigations in the area of Vapor

and Trace Detection of Explosives. In addition specialist with high experience in terrorism and forensic scientist should give a strong and necessary impulse for the further effort in development of techniques for the detection of explosives a preventive way. Because of the complexity of the problem and the very high number of different methods used for the detection of explosives it seemed to be impossible to cover all aspects, methods and techniques during one ARW. Therefore this first ARW shall focus on: Vapor and Trace Detection of Explosives.

SCOPE
The main goals of the proposed Workshop are to: 1. provide an opportunity for scientists and practitioners from West and East to exchange their knowledge and experiences in vapor and trace detection of explosives as preventive measures terrorism; 2. establish new links between potential end-users of detection devices and the scientific community in order to better understand the existing technologies and practical requirements; 3. review the state-of-the-art techniques developed so far in the area of vapor and trace explosives detection, and lay down a research program to achieve the required parameters of detection devices, based on the international cooperation between research groups and organizations from NATO-members and Partner countries. to overcome

PROGRAMME, TIMETABLE AND ORGANIZATION 1st day a.m. Opening remarks, announcements
Vice president RAS Academician N. Laverov

6. R. Sleemann 7. B. Halkett Lunch p.m.

The detection of explosives from boarding passes Freight screening trace detection

11.55-12.25 12.25-12.55 12.55-14.15

Y. Chaplygin, A. Saourov 1. M. Nieuwenhuizen

Words of welcome

9.00 - 9.15 9.15 9.40

Electronic nose and dogs nose 8. St. Nicklin 9. M. Stancl Canine detection Detection of traces of explosives by means of sniffing Dogs 14.15-14.45 14.45-15.15 15.15-15.30

Welcome Speech and Introduction to the NATO Science Program Vapor detection of explosives for counter-terrorism

2. M. Krausa

9.40-10.10

Coffee break

3. A. Resnev Techniques for explosive detection design and investigations perspectives Coffee break (additional registration) Overview and needs 4. H. Schubert Detection of Explosives for Terrorist-Bombs and Landmine Clearance Different Applications of Similar Methods Trace Explosive Collection and Detection

10.10-10.40

10.40-10.55

10. R. Fjellanger REST-a method for 15.30-16.00 detection of explosive hemical substances 11. J. Goschnick Potentials and Requirements 16.00-16.30 for an Electronic Nose to be used as vapour-based detector of explosive packages Discussion of the first day 2nd day a.m. Sensor and methods for trace and vapour detection of explosives 16.30-17.00

10.55-11.25

5. L. Malotky

11.25-11.55

1. S. Smirnov 2. G. Holl

Investigation of properties. of marking and their application Development and Characterization

9.00 - 9.25 9.25 - 9.50

of Explosive-Standards for Training and Testing of Vapor-Phase-Detectors 10. D. Groves 3. I. Buryakov The analytical characteristics of ion mobility increment spectrometery during the detection of explosive vapours and their degradation products 4. Y. Yinon Tracking the terrorists: Identification of explosive residues in post explosion debris by LC/MS methods 9.50-10.15 Development of a Cylindrical Ion Trap Mass Spectrometer f or Explosive Trace Detection 14.55-15.20

Coffee break 10.15-10.40

15.20-15.35

11. V. Kapustin New drift-spectrometer with 1 15.35-16.00 the surface ionization of the organic molecules 12. A. Resnev Discussion of devices development perspective and poster section 16.00-16.30

Coffee break 5. V. Gruznov 6. P. Mostak High-speed portable gas analysers for detection of explosives Vapour and trace detection of explosives

10.40-11.10 11.10-11.40 11.40-12.05 12.05-12.30

General discussion, results and future aspects

16.30-17.30

7. A. Chistjakov A laser spectrometer of ion trap mobility for detection of super small densities of explosives 8 V. Kratasyuk

The development of 12.30-13.00 bioluminescent express-alarm assays for explosives detection with the experience of water ecosystems monitoring as a basis 13.00-14.30

Lunch p.m. 9. S. Alimpiev

Surface Assisted Laser Desorption 14.30-14.55 Ionization (SALDI) technique for trace detection of explosives

List of participants
1. 2. Dr. Krausa M. Dr., Prof. Resnev A. Dr., Prof. Alimpiev S Dr., Prof. Bely Y. Dr. Buryakov I. Dr., Prof. Chaplygin Y. Ph.D. Ching Wu Dr., Prof. Chistyakov A. Dr. Chubarov M. Degurnov S. Dr. Fjellanger R. Dr. Goschnick J. Dr. Groves D. Dr., Prof Gruznov V. Dr. Halkett B. Dr. Holl G. Dr. Ilyin V. Dr., Prof. Kapustin V. Dr. Karr B. Dr. Kisilev I. Dr., Prof. Kratasyuk V. Acad. Laverov N. Dr., Prof. Lopota V. Dr. Prof. Luchinin V. Ph.D. Malotky L. Dr. Maksimov E. Dr. Moseev Y. Dr. Mostak P. Dr. Myasnicov V. Dr. Nicklin St. Co-Director (Germany) Co-Director (Russia) (Russia) (Russia) (Russia) (Russia) (USA) (Russia) (Russia) (Russia) (Norway) (Germany) (UK) (Russia) (UK) (Germany) (Russia) (Russia) (USA) (Russia) (Russia)
(Russia)

3. 4.
5.

31. 32. 33. 34. 35. 36. 37.

38. 39.

6. 7. 8. 9.
10. 11.

40. 41.
42.

43. 44.
45.

12. 13. 14. 15. 16. 17.

18.

46.

Dr. Nieuwenhuizen M. (Netherlands) Dr. Romanenko Y. (Russia) Dr., Prof. Saourov A. (Russia) Dr., Prof. Schubert H. (Germany) Dr., Prof. Sakovich G. (Russia) Dr. Semeykin N. (Russia) Dr. Sleemann R. (UK) Dr. Smirnov S. (Russia) Dr. Smirnov V. (Russia) Dr. Stancl M. (Czech republic) Dr., Prof. Valyaev A. (Russia) Dr., Prof. Vorozhtsov A. (Russia) Dr., Prof. Yinon J. (USA) Dr. Yudin V. (Russia) Yakovlev N. (Russsia) Dr., Prof. Zarko V. (Russia)

19. 20.
21.

22. 23.
24.

25. 26. 27. 28. 29. 30.

(Russia) (Russia) (USA) (Russia) (Russia) (Czech republic) (Russia) (UK)

Vapor detection of explosives for counter-terrorism

M. Krausa Fraunhofer-Institut fr Chemische Technologie (ICT) The September 11th disaster on the twin towers was one of the most terrible terrorist attacks worldwide. It was the temporary high point of numerous horrible attacks during the last years. Very often explosives are involved in these attacks, e.g. World trade center 1993, Oklahoma City 1995, Moscow 1999 and 2002, in addition chemical warfare agents are used for terror attacks also e.g. Tokyo 1995. To protect society against such attacks the detection of explosives is an important requirement. There are several draw backs which hinders the fast and easy vapor detection of explosives. The vapor pressures of the explosives are very low. The number of possible and different explosives is high. The composition of the investigated gas phase differs in dependence of temperature, moisture and chemical composition. In addition the chemical composition is influenced by the special surrounding, e.g. airport hall, basement, buses etc.. Moreover the prevailing package (e.g. hard top case, suicide bombers, letter bomb, etc.) of the explosive influences the detection. Because of these different conditions in

Abstracts

connection with the small vapor pressures of the explosives the chemical smelling is a demanding scientific problem. Up to now so called sniffer dogs are the most successful and widespread systems for the explosives detection at airports and in public areas. Dogs are able to detect explosives under various conditions. On the other hand dogs are living beings and their behavior and skills are influenced by numerous parameters (e.g. age, sex, trainer, daily condition, etc.). To overcome these problems concerning the detection of explosives and illicit substances by dogs chemical sensors seemed to be a valuable alternative for this application. The presented paper describes and discusses necessary requirements of chemical sensor systems for the vapor detection of explosives on the basis of results received by the investigation of sniffer dogs and on information of the concentration and composition of the gas phases. A brief overview of chemical methods for the trace and vapor detection of explosives will be given.

Methods of detection of vapor and trace of explosives: state of the art and perspectives of investigations and development
A. Reznev RF Commission for ICAO The opportune detection and neutralization of explosive devices is important constituent of complex measures on terroristic act prevention. The development of technical means which are intended to detect explosive devices now is one of the actual problems of antiterrorist subdividing activity increasing. The considerable role among these means is played with means of detection of explosives constituting an integral part of any explosive device. The special role belongs to technical means and methods of explosives detection, and particularly explosive vapor or trace, that the latter are the unique direct signs of an explosive device presence in suspicious object. Considering a problem of improving technical means for explosives detection, including their trace and vapor, it is necessary to state a number of

system problems the adequate solution of which is the basis for defining the strategy and ways to increase the efficiency of technical means. These problems are the following: - how the sensitivity of apparatus for explosive vapor or trace detection corresponds with a probability of the explosive device detection at given limitations on decision time and set of the external factors and conditions? - what are the tactical advantages and disadvantages of vapor and trace detection methods as contrasted to X-ray, nuclear and other methods of explosives and explosive devices detection? - what are the place and role of instrument methods for explosive vapor and trace detection in the complex monitoring of the contents of dangerous objects with the aid of combination of different technical means? In the report on examples of existing methods and technical means the indepth study of listed problems is carried out. On the basis of this analysis the main directions for improving tactical and operational characteristics of vapor and trace analysis equipment are formulated. The review of these directions development in the Russian investigations and designs is given. The necessity of a complex systematical approach to the problem is declare. In this way the principals of an equipment integration are justified.

Detection of Explosives for Terrorist-Bombs and Landmine Clearance -- Different Applications of Similar Methods
H. Schubert Fraunhofer ICT Pfinztal , Germany This paper describes the difference of explosive charges using for landmines and terroristic purposes concerning environment, conditions of detectionprocedure, placing, confinement and composition of the explosive charges. The result of this consideration will be : In some cases the known methods of landmine detection is easier to apply for the detection of terrorist charges, in many other cases the task to be full filled will be much more difficult. In some cases up to date no methods for detection are known.

Trace Explosive Collection and Detection

L. Malotky Transportation Security Administration Department of Homeland Security USA Successful research has led to the development and fielding of thousands of explosive trace detection systems at airports and other strategic locations around the world. Scientists have determined that detectable residues of explosives are present on and near improvised explosive devices. The challenge facing us today is how to efficiently and effectively activate, displace, move and recollect these few nano grams of explosives aggressively bound to surface so that we can use them to detect a terrorists explosive device. Over the years researchers have employed a number of approaches to activate the low vapor pressure military explosives to make them detectable. Heat lamps, vibration, air cannons and physical wiping have all been tried and are being reinvented by new research teams. Ablation with dust and CO 2 pellets, hot humid gasses (as the dog uses) or optical methods have been proposed but not reduced to practice. The challenge facing the trace detection community is not the sensitivity or specificity of the trace detectors but rather the engineering and materials science challenge of moving the explosive trace sample from where it is stuck on the bag or person to the detector.

produced were drawn into a triple quadrupole tandem mass spectrometer and were monitored in MRM mode. The infrared unit integrated with the tandem mass spectrometer has demonstrated limits of detection of less than 100 pg for the explosives studied (TNT, NG, PETN and RDX). A background study into the levels of explosives residues on used boarding passes was conducted by analysing over 20,000 boarding passes from a number of airports in England, America and Canada. Traces of explosives were detected on approximately 0.5% of passes analysed. Nitroglycerine contributed to the majority of the positive signals observed. All the signals observed were below 1ng. An automated unit has been developed after the success of the manual feed system, which incorporated the inclusion of a transport mechanism to move the boarding cards through the desorption window automatically. The description efficiency of the system was found to be between 70% and 100%, depending on the thickness of the card used for assessment. The unit was able to handle a throughput rate of 1000 boarding passes per hour and was able to detect between 10pg and 50pg of explosives residue from the surface of the card depending on the compound used.

Freight screening using trace detection

B. Halkett, M. Groves The FLORENCE Project Security Processes Ltd Freight screening using trace detection is difficult but apart from expensive technologies such as PFNA, it is the only technology which will positively discriminate between explosive and other organic materials. Sample acquisition is the key to any trace detection operation: no sample = no detection. This paper discusses sample acquisition from freight vehicles and containers and the ways in which samples can be used from dogs trained to the UKs RASCO technique to technology based detectors. This raises the issue of how auditable and repeatable calibration and training materials can be produced for these detection / analysis systems.

The Detection of Explosives Residues from Boarding Passes

R. Sleeman*, S. Richards*, I. Burton*, J. Luke*, W. Stott**, W. Davidson** * Mass Spec Analytical Ltd. ** Sciex, MDS Inc., Canada A prototype system for the detection of trace explosives residues on aircraft boarding passes has been developed. The desorption of explosives from the passes was achieved using short wave infrared radiation. The vapors

Analysis of Explosive Vapor Emission to Guide the Development of Vapor Detectors

S. Dixon, D. Groves*, P. Cartwright, S. Cairns , M. Brookes and S Nicklin Detection Department, Defence Science and Technology Laboratory, UK Canine olfaction is currently the most effective technique for explosive vapor detection. Development of sensitive vapor detection instrumentation is underway worldwide to provide a similar or even enhanced (e.g. quantitative) capability. This development would be greatly assisted if the mechanism by which canines achieve explosive detection were more fully understood. The specific aim of this fundamental program is to determine the relative importance of the various components within the headspace of plastic explosives for canine detection, in particular the role of the low volatile explosive and its associated volatile impurities relative to the more ubiquitous but more volatile hydrocarbons emanating from the binder. The ultimate question to be addressed is whether vapor detection of plastic explosives can be specifically achieved without detection of the explosive itself. To achieve this aim, a set of specially manufactured RDX based plastic explosive samples has been prepared, where each sample lacks one or more components of the full mixture. The headspace of these depleted samples, along with the full composition and the raw ingredients, were then analysed by GC-MS using both dynamic (thermal desorption) and static (SPME) sampling techniques to identify the compounds present and their relative concentrations. Once complete, canines initially trained to detect samples of the whole explosive, were exposed in blind trials to vapours from each of the depleted samples and their responses recorded. Correlation of the canine and instrumental results has allowed deduction of the relative importance of the components used by the canine for detection. Work is currently underway to further isolate individual compounds from each of the components and to build up increasingly complex mixtures to present to the canines. The presentation will describe the results of the study and the implications for the

development of the next generation explosive vapor detector, impacting techniques such as remote air sampling for canine olfaction, e noses and mass spectrometry. The implications for canine detection and training will also be discussed.

Detection of traces of explosives by means of sniffing dogs

M. Stancl Research Institute of Industrial Chemistry Czech Republic The contribution is focused on our experience with detection of hidden explosives, marked explosives and marking taggant by means of sniffing dogs. The capabilities of sniffing dogs were tested under different conditions to find hidden samples of explosives, releasing traces of vapours or particles. 11 samples of basic types of explosives, including DMNB taggant, were sought by sniffing dogs within the framework of five examination scenarios. The results obtained enable to make certain conclusions concerning the work of dogs in the field of detection of explosives.

REST a method for detection of explosive and chemical substances.

R. Fjellanger NOKSH AS Norway REST (Remote Explosives Scent Tracing) is a detection concept for odor in which air from suspect locations is vacuumed through a polyvinyl chloride (PVC) netting filter. The filters are transferred to dogs trained to signal target odor at extremely low detection thresholds. Applied to the detection of landmines, this involves vacuuming an area of land suspected to contain mines. It will be a description of the principles behind, and the results

of, a training program designed to produce REST detection dogs at detection thresholds similar to those obtained on filters from minefields. The training program is based on the following principles: i) to minimize the dependency on the handler, ii) encourage independent search, iii) build extended search by progressively reducing the frequency of positive filters, iv) minimize anticipation of reward due to positive indication event and v) progressively reduce the detection threshold for TNT. In the study the dogs achieved 95% detection reliability. The REST method was as a start developed by the South African government, and put into practical use by Mechem Consultants, a division of Denel, (Pty), Ltd. at the end of the 1980s. The method was first referred to as MEDDS (Mechem Explosives and Drug Detection System). Its primary purpose was to detect drugs, explosives and weapons at border crossing checkpoints. NOKSH AS has further taken this system future, developing it both technically and in the way of using dogs. On June 2000, NOKSH AS entered into a contract with Geneva International Center for Humanitarian Demining (GICHD) for the execution of a study on Vapor Sampling and Analysis as a part of the GICHD mine detection dog (MDD) program. A report was delivered in October 2001. In 2002 the research program was continued by practical experiments testing the method in Bosnia Herzegovina and this year NOKSH AS also play a key role in a similar test program in Angola. These programs have become valuable sources of information on how physical parameters (temperature, humility, etc.) influence on vapor detection when sampling is conducted in an open-air environment. Working with the REST technology, NOKSH AS has gathered insights into how the method could be applied to other and new areas as a detection system. By using existing technology, vapor detection of explosives, the system can be transferred and used directly on other search areas. If the system were supplied with other selective filters (for chemicals and other substances), the REST method can be a prominent detection system for new departments and for the anti-terrorism purposes. REST has become the fastest, most reliable and cost-effective method in humanitarian demining industry searching for mines in mine suspected areas. Searching large areas on a minimum amount of time, while detecting substances in extreme low concentrations, is what the REST method has

demonstrated. Using this method alone or as a supplement to other techniques would be a huge step forward when searching for explosives and chemical threats in vehicles, containers, trains, boats, etc. It can also be used to verify if peoples have been in contact with such substances.

Potentials and Requirements for an Electronic Nose to be used as vapor-based detector for explosive packages
J. Goschnick Forschungszentrum Karlsruhe, Institut fr Instrumentelle Analytik Explosives packages release a characteristic gas ensemble which is detected by sniffer dogs employed to find bombs hidden in unsuspious containments. In view of some draw-backs of sniffer dogs (such as limited working time, limited age span they could be employed, highly costs of a dog squadron) artificial olfaction with an Electronic Nose (EN) might be an alternative. Although the vapor pressures of the explosive itself is at room temperature very low (vppt range for TNT) additives, impurities and package materials have much higher vapor pressures situated in the low or even mid ppb range. The ensemble of vapours released by all of the components of the explosive package makes up an odour bouquet which is some kind of unique fingerprint. This fingerprint is recognized by the sniffing dog and has to be detected by a gas analytical device as well to find explosives. Sophisticated classical gas analytical instruments may be able to perform a high level analysis with sufficient sensitivity for the very low concentrations involved, but these instruments are too spacious and heavy for mobile use onsite. Moreover, from the analytical point of view the EN would be more appropriate to solve the problem because it works like the dogs, detecting the explosive via an integral perception of the vapour ensemble released by explosive packages. Unfortunately, most of the commercial ENs suffer from similar drawbacks concerning spatial requirements and weight as the conventional analytical instruments. Moreover, most of them cannot be operated on-line and the price of more than 50.000 US$ is a considerable hindrance to their use. Recently very few mobile instruments appeared on the

market with even lower prices but their sensitivity is by far insufficient to be used for explosive detection. A novel type of EN has been developed at the Institute of Instrumental Analysis of the Karlsruhe Research Center which is designed to meet the requirements of consumer products: cheapness, smallness and low power consumption combined with appropriate analytical power. The development is based on the unique gradient micro arrays equipped with gas sensitive sputtered thin films of metal oxide (MOX) which sensitively respond to the ambient air composition with their electrical conductivity. The thumbnailsized gradient micro array chip allows low-cost fabrication because all sensor elements are produced at the same time by partitioning a sputtered MO film with many parallel electrodes to measure the conductivity in between. A gradient technique is used to differentiate the sensor segments with respect to the selectivity of their gas response. The standard micro array chip comprises 38 sensor segments and 4 rear meander heaters to enable an operation at 200400C. A beverage can-sized demonstrator of only 600g weight, the Karlsruhe Micronose (KAMINA), has been developed which is a complete EN system to be used in mobile operations with p-controlled electronics providing operation and on-line data evaluation with 1Hz. The instrument provides a high discrimination power for gases or odors and allows a fast response time of a few seconds. For most organic as well as inorganic gases detection limits 100 ppb are obtained with the standard sputtered MOX films. However, a new generation of micro arrays is under development equipped with nanogranular layers which seem to be able to detect even 1ppb components. Some first results of micro arrays of this type will be presented and the difficulties for gas discrimination under real conditions will be discussed.

Investigation of Properties of Marking Agents and Their Application

S. Smirnov, V. Ilyin, I. Akhmetov State Research Institute Kristall, Russia

In 1991 there were added four agents to the Convention on Plastic and Elastic Explosives Marking for Their Detection: ethylene glycol dinitrate (EGDN), 2,3-dimethyl-2,3-dinitrobutane (DMNB),oand pmononitrotoluenes (o-, p-MNT). In 2002 o-MNT was excluded according to the inter-state coordinated decision. The addition of marking agents was caused by the fact that widely used plastic and elastic explosives based on RDX and PETN were not amenable to detection with searching instruments, based on gas analysis techniques. Vapor pressure of these explosives within the -20oC + 50oC temperature range is from 10-13 to 10-6torr. For comparison, we may mention that o- and pMNT within the same temperature range have vapor pressure from 10-3 to 101 torr and DMNB has 10-610-1torr. Originally all the marking agents used in explosives had the 0.5 wt. % concentration. At present time the increase of DMNB up to 1.5 2.0 wt. % is considered in order to retain it in a composition within the whole guaranteed term. The investigations showed the possibility to detect a marking agent vapor above the surface of marked with it plastic or elastic explosives using gas analysis techniques based on chromatography, mass spectroscopy and drift spectrometry. The results were verified in airports by placing marked explosives into baggage. Large investigation was carried out aimed at marked explosives properties and the results showed identity of their operational properties. There was investigated dynamics of marking agents emission from samples with different geometry (briquette, sheet, cord and etc.) and determined the conditions of their keeping for a long time. It was shown that the necessary concentration of marking agents in explosives can be supported using suitable packing. There was also considered the necessity and possibility of marking a wide range of explosives that were not plastic and did not fall under the action of the Convention. This was caused by the fact that in spite of its good ability to be detected TNT possesses rather high ability to sorption on things contained in baggage and there could be no emission of its vapor. Besides there, exists a wide range of commercial explosives that do not have the searching symptoms necessary for gas analysis techniques. To this range water emulsion and water suspension explosives belong that are widely used

at present. The investigations that were carried out indicated the possibility to use marking for the most widely used explosives. Alongside with mentioned results it was shown that to increase the reliability of detection it is necessary to improve sensibility of equipment. And there should be realized at least two trends: - development of new instruments that have significantly higher sensitivity to adopted marking agents than available at present; - continuation of searching for new marking agents that make higher the sensitivity of existent instruments. But it is obvious that more correct is the third trend - search for new principles of vapor detection and development new marking agents for them providing their maximum sensitivity.

calculate the service life of this standards. The MPKs have authentic properties of explosives but are non-hazordous when been tested in approved hazards classification tests. The chemical vapor signatures of different explosives have been verified by instruments and canine (K-9) detection in a round-robin test.

The Analytical Characteristics of Ion Mobility Increment Spectrometer During the Detection of Explosive Vapors and Products of Their Degradation
I. Buryakov The Design & Technological Institute of Instrument Engineering for Geophysics and Ecology (IDE), the Siberian Branch of RAS, Russia The operational detection of trace quantities of explosive vapors and products of their degradation (EV) in air is the complex analytical problem. High demands placed on device sensitivity and selectivity are dictated by a rather low vapor pressure of the compounds, their high adsorption power and interfering components present in air in large quantities. Ion mobility increment spectrometer (IMIS) is one of the instruments of those satisfying these requirements. Like an ion mobility spectrometer (IMS), the operation of IMIS rests on sampling air containing a mixture of trace constituents, its ionization spatial separation of produced ions and separated ions detection. IMIS differs from IMS in that ions of different types are separated in IMIS by ion mobility increment that depends on electric field strength. In this work are investigated the possibility of the selective registration of vapors of 2,4-dinitrotoluene, 2,4,6-trinitrotoluene, pentaerythritol tetranitrate, 1,3-dinitrobenzene, 1,3,5-trinitrobenzene with the aid of IMIS with different humidity of air, in the presence of vapors of gasoline, diesel fuels, ammonia. The calculated detection limit, sensitivity, linearity and speed of response of IMIS on detecting vapours of the abovementioned compounds have been determined.

Development and Characterization of Explosive-Standards for Training and Testing of Vapor-Phase-Detectors

G. Holl Bundeswehr Research Institut for Materials, Explosives, Fuels and Lubricants We report on an application of using standard devices with explosives in order to produce calculated and authentic odor-signatures to investigate the sensitivity and selectivity of different chemical sensors for detecting explosives from the vapor phase. We achieved this aim by placing small quantities of explosives on a well defined inert metal surface (micro-mass-test sample MPK) without changing the chemical composition of the standard material. We evaluated the emission rate of the explosive related chemicals (ERC) with temperature and different surfaces. With this data we were able to

Tracking the Terrorists: Identification of Explosive Residues in Post-Explosion Debris by LC/MS Methods.
J. Yinon National Center for Forensic Science, University of Central Florida, Orlando, USA One of the tasks in the investigation of a terrorist bombing is to identify the type of explosive used in the bombing and if possible, its origin. This kind of information will assist the investigators and possibly lead to the apprehension of the suspects. The explosives used in terrorist bombings come from various sources, such as standard military explosives (stolen from military installations), commercial explosives used in mining and construction, explosives taken from landmines which were dug up, and improvised explosives, including manufacture of explosives in clandestine laboratories. It is therefore of major importance to be able to identify and characterize the explosive residues, which in many cases are found in minute amounts. We have studied several groups of explosives, including nitroaromatic explosives (such as TNT), nitramine explosives (such as RDX),nitrate ester explosives (such as nitroglycerin and PETN) and inorganic oxidizers (such as ammonium nitrate). We have found that the analytical method of choice for identification and characterization of all studied explosive residues -from the point of view of sensitivity and selectivity- is LC/MS (both electrospray ionization and APCI). The instrument used was a Thermo-Finnigan LCQ-DUO LC/MS/MS system. The HPLC consisted of a Restek, Allure C18 column, with methanolwater or methanol-isopropanol-water as mobile phase in the isocratic or gradient mode. MS/MS was used for further confirmation of identified ions.

A method has been developed for characterization and origin identification of 2,4,6-trinitrotoluene (TNT) by means of its by-product isomer profile, using LC/MS-APCI in the negative-ion mode. These isomers include isomers of trinitrotoluene, dinitrotoluene, trinitrobenzene and dinitrobenzene, which are all by-products in the industrial production process of TNT. This profile was found to be different for various production sites. Nitrate ester explosives (EGDN, NG and PETN) were studied by ESIand APCI-LC/MS, using post-column additives. Explosives in mixtures could be identified at levels down to 5 ppb. Formation processes of adduct ions in electro spray mass spectrometry (ESI-MS) of RDX were studied and origin of these adduct ions was determined. Inorganic salts have been used extensively as oxidizing agents in various explosive mixtures, such as ANFO, dynamites, etc. We have studied a group of inorganic oxidizers and found that under certain conditions (temperature of heated capillary and selection of positive- vs. negative-ions) it is possible to identify these oxidizers by ESI-MS. These compounds produced cluster ions, which contained the entire oxidizer molecule. Isotopically labelled compounds and MS/MS were used to confirm the suggested ionic compositions.

High-Speed Portable Gas Analyzers for Explosives Detection

V. Gruznov, M. Baldin, I. Buryakov, V. Filonenko The Design & Technological Institute of Instrument Engineering for Geophysics and Ecology of the Russian Academy of Sciences, Siberian Branch (IDE RAS), Russia

The IDE is engaged in the development of the technologies of highspeed gas chromatography, ion mobility increment spectrometry, chromatomass-spectrometry and the design of high-speed portable devices for explosives detection.

High-speed gas chromatographs are developed with the use of new multicapillary columns that ensure explosives separation in 10-60 s. Efficient independent vortex samplers are developed. The sampler permits one to gather samples at a distance of 0-20 cm from the surface tested. Examples for the use of the vortex sampler for inspecting a car and a vault are given. Modes of high-speed sampling, sample injection and separation are realized in high-speed portable gas chromatographs of EKHO-series (EKHOM, EKHO-EW) that can perform a great number of analysis on detecting trace amounts of explosives. Specifications of the EKHO-M device: detection limit for 2,4,6-TNT is 10-14g/cm3; time of 2,4,6-TNT vapor analysis at a column temperature of 175C is no more than 15 s; time of a concentrator sampling on detecting TNT traces at an air temperature of 29-25C is 15-60 s. A development of the EKHO-M is an EKHO-A chromatograph using air as a carrier gas, which enhanced the device usability under field conditions. The possibilities for the MCC operation with air as a carrier gas are shown, a new ion detector with a varying selectivity and a filter for air purification are developed. To enhance detection selectivity with a high speed of the compound identification a mobile chromato-mass-spectrometer (MCMS) is developed. NIST/EPA data base containing to 120 thousand compounds is used for mass-spectra interpretation. For parameters setting and results processing an external IBM PC is used. The detection time and sensitivity of the MCMS are much the same as of gas chromatographs To enhance speed of response of the explosives detector-analyzers a technique of ion mobility increment spectrometry is developed. A possibility to detect TNT traces at a concentration of 10 -14 g/cm 3 in several minutes without pre concentration is shown. The development of spectrometric detectors could further enhance sensitivity and speed of response of portable devices.

AliaChem a.s., Division, Synthesia Vupch, Czech Republic Vapour detection and trace detection of explosives are two basic methods of explosive detection. The boundary conditions in vapour detection and trace detection are discussed. The main advantage of vapour detection is a quick and operational easy search of objects, persons and buildings by hand- held detectors. The substantial problem is the temperature dependence of explosive vapour pressure. The limits of vapour detection at low temperature are demonstrated and discussed. The trace or particle detection is not so quick and operational suitable but this method is independent on temperature conditions. Usually, one particle found and inserted in a detector inlet is sufficient for positive detection. The synergy of simultaneous use of vapour and trace detection can substantially increase the effectiveness of explosive detection. The further increase of sensitivity of detectors is required. MEMS/NEMS sensors can solve this problem in future in combination with good pre concentrators. The possibilities of biological sensors are not fully explored and we can expect a better exploitation not only of the high sensitivity of dog and other animals but also the ability of assessment and understanding of percepts obtained.

Laser Ion Mobility Spectrometry for Detection of Ultra Low Concentration of Explosives
A. Chistyakov Moscow Engineering Physics Institute (State University) The new approach to a problem of detection of ultra low concentration of explosives is offered in our work. It is based on a combination of non equilibrium laser ionization and the modernized spectrometry of ion mobility. The carried out cycle of researches of nitro-compounds multi photon ionization has shown high efficiency of this method as a source of ions for spectrometry of ion mobility. Investigations of ionization by SALDI method, and laser induced surface ionization of explosive molecules are carried out.

Vapour and Trace Detection of Explosives

P. Mostak

On the basis of researches the breadboard model of portable laser spectrometer of ion mobility for detection of explosives with sensitivity in air at a level of 10-14 10-15 g/cm3 has been developed.

The Development of Bioluminescent Express-Alarm Assays for Explosives Detection with the Experience of Water Ecosystems Monitoring As Basis
V. Kratasyuk, J. Gitelson, E. Esimbekova Krasnoyarsk State University, Institute of Biophysics, Siberian Branch of the Russian Academy of Sciences Bioluminescence has a number of properties that make it particularly advantageous for detection of toxic chemicals. It is based on the transformation of chemical bond energy into visible radiation with high efficiency, which is driven by a class of enzymes generically termed luciferases utilizing substrates generically called luciferins. New methodology for biophysical methods of contact monitoring of aquatic ecosystems have been suggested. New highly sensitive and rapid bioluminescent assays for estimating the state of natural ecosystems have been developed. The presence of toxic agents in the environment is determined by variations in the following bioluminescence parameters: luminescence intensity, luminescence decay constant, and the time needed for luminescence to reach its maximum. The degree of toxicity is estimated qualitatively, based on the differences in the results of the test for the analyzed and the control samples. The enzymatic bioluminescent tests have the following characteristics: high specificity or integrated response, the time of the analysis is not more than 3-5 min, high sensitivity to toxic substances (up to 10-14 moles of analyte), a simple measurement procedure, the availability of reagents, and a broad market of bio luminometers. It is well known that 2,4 - dinitrofluorobenzene are effective inhibitors of coupled bioluminescent system: NADH:FMN-oxidoreductase-luciferase. Therefore, it is possible to evaluate the presence of explosives in environment using bioluminescent assay. The coupled and triple bioluminescent assays

may be adapted to the detection of explosives in the case of terrorist acts. Because of the specific nature of these reactions it is possible to develop a broad range of coupled enzyme systems to indicate the presence of explosives. Thus we plan to optimize the detecting systems through a) varying the substrates or enzyme concentration, b) varying the type and mechanism of interaction in polyenzyme reactions, and c) final selecting the bioluminescent systems that would be the most effective in determination of the toxic substances. These assays has great promise to reduce the risks of terrorist activities to civilian and military personnel. Our extensive experience and expertise will accelerate the development of the Bioluminescence Signal Assays prototype technologies. It is envisioned that some format would be utilizable in First Responder applications.

Development of a Cylindrical Ion Trap Mass Spectrometer for Explosive Trace Detection
S. Cairns, N. Alcock, P. Cartwright & D. Groves* Detection Department, UK Explosive trace detection is an established part of security screening used by a number of government bodies worldwide. Accomplished either through the detection of vapours emanating from the explosive or the detection of particulate residues, technologies deployed for this application have included fast gas chromatography/chemiluminescence (GC/CL) and ion mobility spectrometry (IMS). Whilst effective, these technologies have a number of limitations including limited flexibility in responding to new threats, limited dynamic range and relatively poor specificity. There is a requirement therefore for the new generation of portable detectors with enhanced performance for a wider range of compounds.

Mass spectrometry (MS) is under evaluation for the development of the next generation of explosive trace detectors due to its high specificity and almost universal detection capability. However, mass spectrometers are traditionally viewed as large, power hungry instruments, better suited to the laboratory than field use. The effectiveness of MS for explosive detection and analysis is well proven; the challenges therefore are primarily to miniaturise and ruggedise the technology sufficiently for field use. This work describes the development of a cylindrical ion trap mass spectrometer (CITMS) to act as a portable MSED (mass spectrometry explosive detector) technical demonstrator. Development has focused on the development of the CIT mass analyser, Rf circuitry, ionisation source and miniaturisation using the architecture of a commercial ion trap instrument. Results of the characterisation of this portable instrument with a gas chromatography (GC) inlet are presented. An outline of the future development will be given.

New Drift-Spectrometer with the Surface Ionization of the Organic Moleculs.

V. Kapustin. Join-stock Company GYCOM Moscow, Russia In accordance with our new physical model the ionization of the organic molecules on the complex oxides surface is the result of the molecules interaction with the asid-type [ACB] and the base-type [BCB]. Brensted centers and with the alkaline ions on the oxides surface [AMI]. These processes occurs with the secondary ions generation and its following desorption according with these reactions: [ACB] + ( M R) M+ + ( R + H )gas , [ACB] + M (M + H)+ ( M - H )+ + H2gas , [BCB] + ( + )- ( - )- +2gas , [AMI] + M (M+Na)+ (M-R-H-Na)+ +(R+H)gas.

The [ACB] and the [BCB] centers are generated on the oxides surface in the H+ and OH- ions form owing to the water molecule adsorption under air conditions. Developed physical model was used in our experimental investigations of novocain, dimedrol, bencain, papaverin and hinin surface ionization on the oxides Mo surface at the atmospheric air conditions as well as TNT, RDX, PETN, HMX and TETRYL surface ionization on the oxide bronze surface at the atmospheric air conditions too. The theory of the intensive ion beam drift motion at the atmospheric pressure air was developed. It was shown, that the value Pi= j/ 0vg2, where , j and vg are ions mobility, current density and axial ions velocity along the gas flow, proved to be the ion purveyance. The new type of the ion driftspectrometer was developed. It contains the big surface area flat surfaceionization emitter, whereby, the first, the sensibility of the drift-spectrometer was increased by two or three orders of magnitude in comparison with known devices and, the second, it enabled us to investigate the molecules surface ionization characteristics under known value of the electric field near the emitter surface. Due to the new type of the ion drift-spectrometers it was possible to measure the dependences of the molecules ionization activation energy upon the organic molecules concentration, to measure the integral efficiency and reaction order of the molecules surface ionization as well as the non-linear part of the organic molecules ion drift mobility in accordance with the wellknown equation = 0(1+ 2), where is the electric field. The developed device can be used for vapor and trace detection of explosives and drugs.

NQR-Based Detectors for Explosives The New AntiTerrorist Technology

Y. Bely, N. Semeykin Joint-stock company Scientific-Research Institute of Instrument Design named after V. Tikhomirov(NIP)


A struggle against international terrorism is an actual task nowadays. The main aspect of this task is the detection of explosives at the passengers shipping and luggage loading aboard the aircraft, mail delivery to banks and offices, visitors and staff entering the secret objects and so on. Instruments on the base of nuclear quadruple resonance (NQR) could be effective for detection of explosives and terrorist acts prevention. The identifying method is a particular feature of NQR. Most of explosives consist of nitrogen-14 atoms, which give detection possibility on their NQR signals. The most spread explosives NQR frequency range is 0.55.5 MHz. The advantages of the NQR method:

At the explosives mix detection the NQR instrument could make a detection of any explosives mix component. E. g., and - based mixes could be effectively detected upon the containing hexogen (RDX). When the explosive is in a metallic or metalled case, it couldnt be detected, but at this, NQR detector can fix a presence of metal in the tested object, i.e., it performs selective metal detector functions. The NQR detector application can ensure high detection probability of the explosives with low level of their false detection. At present a safe-type detector with chamber volume of 15 litres is developed for mail items checks. Its function is to detect hexogen, oktogen and (ReTN), and also THT (TNT) in perspective. The detector has high sensibility: a hexogen sample of 25 g is detected in 2 sec with more 98% probability and 1% of false detection probability. At present active works are performed on creation of the conveyor-type explosives detector with chamber volume 140 l for luggage inspection. Full scale tests on the operational dummy instruments has been confirmed the detection ability with high detection features on the small amounts of explosives (25 g of hexogen (RDX)). The achieved results allow to create pre-production samples of the prototype instruments in the shortest period of time, as well as instruments of another classes.

Explosives certain type high selectivity and identification ability. The presence of other components in the studied object and mechanical mixture of the explosives with other components doesnt effect the detectors possibility of the explosives detection, which it is adjusted for. Detection features doesnt depend on the explosives geometric shape Detection ability of non-gasing explosives (plastit and elastit on hexogen (RDX) and (ReTN) base), and hermetically packed explosives samples also. Practically, plastit is undetectable by regular ways (dogs, gas analyzers) of detection. NQR method is non-destructive detection method. The operational density of alternative magnetic field doesnt corrupt data, stored on the magnetic media. NQR method is a direct method and doesnt need instrument calibration and results interpretation by the operator. Ionizing radiation lack, equipment safety, application possibility as in stationary as well in mobile performance. Application possibility of NQR instrument together with instruments, based on the different physical principles X-ray check equipment, for example, increases the detection productivity. Detected explosives weight assessment possibility since NQR signal is proportional to the tested sample weight.

Enhancing Efficiency of High-Speed Explosives Vapor Concentration Gruznov V.M., Leonov A.Yu., Filonenko V.G., Shishmarov A.T. The Design & Technological Institute of Instrument Engineering for Geophysics and Ecology of the Russian Academy of Sciences, Siberian Branch (IDE RAS):

One way to enhance detectability of devices used for detecting explosives by their vapor traces in air is preconcentration. Sample enrichment common to available detectors tends to decrease detected concentration by a factor of 10-100, therewith detection limit achieved is 10-14 g/cm3. Such a detection limit ensures a Russian EKHO-M explosives vapor detector in which air is drawn through several layers of metal grid with a low-power pump (to 3 W, air flow rate is 100 cm3/s, concentrator trap diameter is 8 mm). The higher is the air volume drawn through a concentrator with a given trapping capacity, the higher is an enrichment factor achieved. From the analysis of the EKHO-M sampler characteristics it is obvious that with the given pump, grids number and mesh sizes air flow rate through the concentrator could be increased tenfold through a rise in a concentrator diameter by a factor of five; in this case the air flow rate through a separate mesh is kept constant independent of the overall flow rate through the trap. Therefore, the amount of the sample trapped should also increase tenfold. To inject samples from a concentrator with an enlarged diameter (to 40 mm) an injector of the EHKO-M device was provided with an injection device with a sample focusing in a cooled capillary. Experiments have shown that in the EKHO-M device having the injector with the sample focusing response for low volatile compounds, like TNT and PETN, is ten times that of the EKHO -M with a basic injection device. Thus, one could decrease the detection limit of the portable EKHO-M device to 10-15g/cm3 retaining sampling time at 10-15 s and the other characteristics practically unchanged. Further decrease in detection limit at the cost of concentration requires to increase power of a sampling pump and a thermal desorber, especially.

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