Evaluation of canine training aids containment for homemade explosive and components by headspace analysis and canine testing

While canines are most commonly trained to detect traditional explosives, such as nitroaromatics and smokeless powders, homemade explosives (HMEs), such as fuel–oxidizer mixtures, are arguably a greater threat. As such, it is imperative that canines are sufficiently trained in the detection of such HMEs. The training aid delivery device (TADD) is a primary containment device that has been used to house HMEs and HME components for canine detection training purposes. This research assesses the odor release from HME components, ammonium nitrate (AN), urea nitrate (UN), and potassium chlorate (PC), housed in TADDs. Canine odor recognition tests (ORTs) were used with analytical data to determine the detectability of TADDs containing AN, UN, or PC. Headspace analysis by gas chromatography/mass spectrometry (GC/MS) with solid-phase microextraction (SPME) or online cryotrapping were used to measure ammonia or chlorine, as well as other unwanted odorants, emanating from bulk AN, UN, and PC in TADDs over 28 weeks. The analytical data showed variation in the amount of ammonia and chlorine over time, with ammonia from AN and UN decreasing slowly over time and the abundance of chlorine from PC TADDs dependent on the frequency of exposure to ambient air. Even with these variations in odor abundance, canines previously trained to detect bulk explosive HME components were able to detect all three targets in glass and plastic TADDs for at least 18 months after loading. Detection proficiency ranged from 64% to 100% and was not found to be dependent on either age of material.     

Characterization of an odor permeable membrane device for the storage of explosives and use as canine training aids

The storage and use of explosives is regulated at the state and federal level, with a particular focus on physical security and rigorous accounting of the explosive inventory. For those working with explosives for the training and testing of explosive-detecting canines, cross-contamination is an important concern. Hence, explosives intended for use with canine teams must be placed into secondary storage containers that are new, clean, and airtight. A variety of containers meet these requirements and include screw-top glass jars (e.g., mason jars). However, an additional need from the explosive-detecting canine community is secondary containers that can also be used as training aids whereby the volatiles emitted by explosives are emitted in a predictable and stable manner. Currently, a generally accepted method for the storage of explosives and controlled emission of explosive vapor for canine detection does not exist. Ideally, such containers should allow odor to escape from the training aid but block external contaminates such as particulates or other volatiles. One method in use places the explosive inside a permeable cotton bag when in use for training and then stores the cotton bag inside an impermeable nylon bag for long-term storage. This paper describes the testing of an odor permeable membrane device (OPMD) as a new way to store and deploy training aids. We measured the evaporation rate and flux of various liquid explosives and volatile compounds that have been identified in the headspace of actual explosives. OPMDs were used in addition to traditional storage containers to monitor the contamination and degradation of 14 explosives used as canine training aids. Explosives were stored individually using traditional storage bags or inside an OPMD at two locations, one of which actively used the training aids. Samples from each storage type at both locations were collected at 0, 3, 6, and 9 months and analyzed using Fourier Transform Infrared (FTIR) Spectroscopy and Gas Chromatography–Mass Spectrometry (GC–MS) with Solid-Phase Microextraction (SPME). FTIR analyses showed no signs of degradation. GC–MS identified cross-contamination from ethylene glycol dinitrate (EGDN) and/or 2,3-dimethyl-2,3-dinitrobutane (DMNB) across almost all samples regardless of storage condition. The contamination was found to be higher among training aids that were stored in traditional ways and that were in active use by canine teams.     

Cyclic Pentanone Peroxide: Sensitiveness and Suitability as a Model for Triacetone Triperoxide

Research to counter the threat of organic peroxides such as triacetone triperoxide (TATP) is at times hampered by their inherent extreme sensitiveness and volatility. This work describes an approach to lowering some risks associated with the handling of TATP in the laboratory through the use of an analog species, tripentanone triperoxide (TPTP). Sensitiveness has been tested via standard methods. GCMS analysis has shown that TPTP degrades via similar mechanisms to TATP under a range of conditions. Slight differences in product composition were traced to side reactions which may also affect impurities present in homemade TATP synthesis. A pilot field trial was conducted to evaluate TPTP as a substitute for TATP in explosive detection dog (EDD) scent training. The degradation studies have yielded insights into the complexities of the acidic degradation of cyclic peroxides with potential forensic application, and TPTP's inadequacy as a TATP pseudoscent is a valuable example of the limitations of such training aids.     

Sulfuric, hydrochloric, and nitric acid-catalyzed triacetone triperoxide (TATP) reaction mixtures: an aging study

The organic peroxide explosive triacetone triperoxide (TATP) is regularly encountered by law enforcement agents in various stages of its production. This study utilizes solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) to examine sulfuric acid-, hydrochloric acid-, and nitric acid-catalyzed TATP syntheses during the initial 24 h of these reactions at low temperatures (5-9°C). Additionally, aging of the reaction mixtures was examined at both low and ambient temperatures (19-21°C) for a further 9 days. For each experiment, TATP could be readily identified in the headspace above the reaction mixture 1 h subsequent to the combination of reagents; at 24 h, TATP and diacetone diperoxide (DADP) were prominent. TATP degraded more rapidly than DADP. Additionally, chlorinated acetones chloroacetone and 1,1,-dichloroacetone were identified in the headspace above the hydrochloric acid-catalyzed TATP reaction mixture. These were not present when the catalyst was sulfuric acid or nitric acid.     

The Identification of Chlorinated Acetones in Analyses of Aged Triacetone Triperoxide (TATP)

The organic peroxide explosive triacetone triperoxide (TATP) is regularly encountered by law enforcement agents in various stages of its production, storage, or usage. In a previous study, it has been demonstrated that isolated, rigorously purified, TATP may degrade to form a series of chlorinated acetones when directly treated with excess concentrated hydrochloric acid. The current study extends this work to examine whether this phenomenon may be measured during the more feasible scenario of aging of rudimentarily purified TATP contaminated with trace reaction mixture. It was demonstrated that solid-phase microextraction gas chromatography/mass spectrometry analyses of aged TATP that was synthesized utilizing hydrochloric acid catalyst may identify the presence of the degradation products chloroacetone and 1,1-dichloroacetone. Upon aging of TATP synthesized utilizing either sulfuric or nitric acid catalyst, no acid specific degradation products could be identified. These findings may be exploited by forensic chemists in the analyses of TATP samples.     

Headspace concentrations of explosive vapors in containers designed for canine testing and training: theory, experiment, and canine trials

It is a common misconception that the amount of explosive is the chief contributor to the quantity of vapor that is available to trained canines. In fact, this quantity (known as odor availability) depends not only on the amount of explosive material, but also the container volume, explosive vapor pressure and temperature. In order to better understand odor availability, headspace experiments were conducted and the results were compared to theory. The vapor-phase concentrations of three liquid explosives (nitromethane, nitroethane and nitropropane) were predicted using the Ideal Gas Law for containers of various volumes that are in use for canine testing. These predictions were verified through experiments that varied the amount of sample, the container size, and the temperature. These results demonstrated that the amount of sample that is needed to saturate different sized containers is small, predictable and agrees well with theory. In general, and as expected, once the headspace of a container is saturated, any subsequent increase in sample volume will not result in the release of more vapors. The ability of canines to recognize and alert to differing amounts of nitromethane has also been studied. In particular, it was found that the response of trained canines is independent of the amount of nitromethane present, provided it is a sufficient quantity to saturate the container in which it is held.     

Availability of target odor compounds from seized ecstasy tablets for canine detection

The aim of this study was to compare seized samples of 3,4-methylenedioxy-N-methylamphetamine (MDMA) pills, used to train law enforcement detection canine teams, to determine what differences exist in the chemical makeup and headspace odor and their effect on detectability. MDMA solutions were analyzed by liquid chromatography-mass spectrometry. Analysis of these samples showed a wide variance of MDMA (8-25%). Headspace SPME-GC/MS analysis showed that several compounds such as 3,4-methylenedioxyphenylacetone and 1-(3,4-methylenedioxyphenyl)-2-propanol are common among these MDMA samples regardless of starting compound and synthesis procedure. However, differences, such as the level of the various methylenedioxy starting compounds, were shown to affect the overall outcome of canine detection, indicating the need for more than one MDMA training aid. Combinations of compounds such as the primary odor piperonal in conjunction with a secondary compound such as MDP-2-OH or isosafrole are recommended to maximize detection of different illicit MDMA samples.     

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography‐IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)‐IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone–TATP combinations. The extent of negative (δ¹³C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ²H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ¹⁸O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC‐IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound‐specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations.     

Sensitivity of TATP to a TASER Electrical Output

A series of experiments were performed to evaluate and document the effect of a TASER (“stun gun”) on triacetone triperoxide (TATP), an easily manufactured explosive used often in IEDs and suicide bombing vests. TATP samples were synthesized and subjected to several tests of their sensitivity. These samples were run through a BAM Friction test with a result of <0.5 N, Impact Test with a result of 5.8 ± 0.4 cm, and Electrostatic Discharge test with a result of 0.073 ± 0.018 J. In addition, TATP was shocked with a TASER in a variety of configurations. The TATP reacted in 17/17 tests when the TASER arced through the TATP and 0/4 times when the TATP was configured in such a way that the TATP was not subjected to the electrical arc. Based on the experimental data, TATP will readily explode in a variety of configurations by a TASER or similar device. Testing should be expanded, as the data presented here are limited to a single formulation of TATP. Just one of a large array of TASER‐like devices by a single manufacturer were tested; other devices, scenarios and formulations of TATP and other likely threat materials should be assessed.     

Detection of explosives in hair using ion mobility spectrometry

Conventional explosives 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), and ethylene glycol dinitrate (EGDN) sorbed to hair can be directly detected by an ion mobility spectrometer (IMS) in E-mode (for explosives). Terrorist explosive, triacetone triperoxide (TATP), difficult to detect by IMS in E-mode, was detected in N-mode (for narcotics). Three modes of sample introduction to IMS vapor desorption unit were used: (i) placement of hair directly into the unit, (ii) swabbing of hair and placement of swabs (i.e., paper GE-IMS sample traps) into the unit, and (iii) acetonitrile extracts of hair positioned on sample traps and placed into the unit. TNT, NG, and EGDN were detected in E-mode by all three sample introduction methods. TATP could only be detected by the acetonitrile extraction method after exposure of the hair to vapor for 16 days because of lower sensitivity. With standard solutions, TATP detection in E-mode required about 10 times as much sample as EGDN (3.9 mug compared with 0.3 mug). IMS in N-mode detected TATP from hair by all three modes of sample introduction.     

Analysis of Explosives by GC‐UV

A mixture of explosives was analyzed by gas chromatography (GC) linked to ultraviolet (UV) spectrophotometry that enabled detection in the range of 178–330 nm. The gas‐phase UV spectra of 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitrotoluene (DNT), ethylene glycol dinitrate (EGDN), glycerine trinitrate (NG, nitroglycerine), triacetone triperoxide (TATP), and pentaerythritol tetranitrate (PETN) were successfully recorded. The most interesting aspect of the current application is that it enabled simultaneous detection of both the target analyte and its decomposition products. At suitable elevated temperatures of the transfer line between the GC instrument and the UV detector, a partial decomposition was accomplished. Detection was made in real time and resulted in overlaid spectra of the mother compound and its decomposition product. Hence, the presented approach added another level to the qualitative identification of the explosives in comparison with traditional methods that relies only on the detection of the target analyte. As expected, the decomposition product of EGDN, NG, and PETN was NO, while TATP degraded to acetone. DNT and TNT did not exhibit any decomposition at the temperatures used.     

Accumulation of explosives in hair--Part 3: Binding site study

This study extends previous work on the sorption of explosives to the hair matrix. Specifically, we have studied the interaction of 2,4,6-trinitrotoluene (TNT) and triacetone triperoxide (TATP) as a function of chemical pretreatment with acetonitrile, neutral and alkaline hydrogen peroxide, methanolic KOH and potassium permanganate, and the morphological changes that accompany these treatments. While differences in vapor pressure can account for quantitative differences between TNT and TATP sorption, both are markedly affected by the chemical rinses. Examination of the hair surface shows different degrees of smoothening following rinsing, suggesting that the attachment to hair is largely a surface phenomenon involving the 18-methyleicosanoic acid lipid layer. Density functional theory calculations were employed to explore possible nucleation sites of TATP microcrystals on the hair. We conclude that some of the sites on melanin granular surfaces may support nucleation of TATP microcrystals. Moreover, the calculations support the experimental finding that dark hair adsorbs explosives better than light hair.     

The Differentiation of the Volatile Organic Signatures of Individuals Through SPME-GC/MS of Characteristic Human Scent Compounds

Abstract:  Human scent evidence is utilized as an investigative tool through canine scent discriminations based on the premise that human scent is an individualizing characteristic. This study describes the development of what is effectively a human scent barcode consisting of the relative ratios of an individual's "primary odor" compounds utilized to determine a reproducible and individualizing profile which can be stored in a searchable database for a proof of concept of human scent as a biometric measure. Triplicate hand odor samples were evaluated from 10 subjects utilizing solid phase micro-extraction gas chromatography/mass spectrometry (SPME-GC/MS) and compared via Spearman Rank Correlations. Narrowing the compounds considered for each subject to only those common in all three samples, or a subject's "primary odor constituents," produced a greater degree of both individualization and discrimination; at both correlation thresholds of 0.9 and 0.8, the individuals were correctly discriminated and identified in 99.54% of the cases.     

Performance evaluation of the Scent Transfer Unit (STU-100) for organic compound collection and release

The Scent Transfer Unit (STU-100) is a portable vacuum that uses airflow through a sterile gauze pad to capture a volatiles profile over evidentiary items for subsequent canine presentation to assist law enforcement personnel. This device was evaluated to determine its ability to trap and release organic compounds at ambient temperature under controlled laboratory conditions. Gas chromatography-mass spectrometry (GC-MS) analyses using a five-component volatiles mixture in methanol injected directly into a capture pad indicated that compound release could be detected initially and 3 days after the time of collection. Additionally, 15 compounds of a 39-component toxic organic gaseous mixture (10-1000 parts per billion by volume [p.p.b.(v)]) were trapped, released, and detected in the headspace of a volatiles capture pad after being exposed to this mixture using the STU-100 with analysis via GC-MS. Component release efficiencies at ambient temperature varied with the analyte; however, typical values of c. 10% were obtained. Desorption at elevated temperatures of reported human odor/scent chemicals and colognes trapped by the STU-100 pads was measured and indicated that the STU-100 has a significant trapping efficiency at ambient temperature. Multivariate statistical analysis of subsequent mass spectral patterns was also performed.     

Creation of training aids for human remains detection canines utilizing a non-contact, dynamic airflow volatile concentration technique

Human remains detection (HRD) canines are trained to locate human remains in a variety of locations and situations which include minimal quantities of remains that may be buried, submerged or extremely old. The aptitude of HRD canines is affected by factors such as training, familiarity with the scent source and environmental conditions. Access to appropriate training aids is a common issue among HRD canine handlers due to overly legal restrictions, difficulty in access and storage, and the potential biological hazards stemming from the use of actual human remains as training aids. For this reason, we propose a unique approach of training aid creation, utilizing non-contact, dynamic air-flow odor concentration onto sorbent materials. Following concentration, the sorbent material retains the odor from the scent source composed of volatile organic compounds. The sorbent material containing the odor can then be utilized as a canine training aid. Training materials prepared in this manner were tested under a variety of conditions with many HRD canines to demonstrate the efficacy of the new training aids. A high level of correct canine responses to the new training aids was achieved, approaching 90%, with minimal false positives.     

Decomposing Human Blood: Canine Detection Odor Signature and Volatile Organic Compounds

The admissibility of human “odor mortis” discrimination in courts depends on the lack of comprehension of volatile organic compounds (VOCs) during the human decay process and of the lack in standardized procedures in training cadaver dogs. Blood was collected from four young people who died from traffic accidents and analyzed using HS‐SPME/GC‐MS at different decompositional stages. Two dogs, professionally trained, were tested to exactly locate blood samples, for each time point of the experiment. We found a long list of VOCs which varied from fresh to decomposed blood samples, showing differences in specific compounds. Dog performance showed a positive predictive value between 98.96% and 100% for DOG A, and between 99.47% and 100% for DOG B. Our findings demonstrated that decomposing human blood is a good source of VOCs and a good target for canine training.     

Odor analysis of decomposing buried human remains

This study, conducted at the University of Tennessee's Anthropological Research Facility (ARF), lists and ranks the primary chemical constituents which define the odor of decomposition of human remains as detected at the soil surface of shallow burial sites. Triple sorbent traps were used to collect air samples in the field and revealed eight major classes of chemicals which now contain 478 specific volatile compounds associated with burial decomposition. Samples were analyzed using gas chromatography-mass spectrometry (GC-MS) and were collected below and above the body, and at the soil surface of 1.5-3.5 ft. (0.46-1.07 m) deep burial sites of four individuals over a 4-year time span. New data were incorporated into the previously established Decompositional Odor Analysis (DOA) Database providing identification, chemical trends, and semi-quantitation of chemicals for evaluation. This research identifies the "odor signatures" unique to the decomposition of buried human remains with projected ramifications on human remains detection canine training procedures and in the development of field portable analytical instruments which can be used to locate human remains in shallow burial sites.     

Evaluation of vapor profiles of explosives over time using ATASS (Automated Training Aid Simulation using SPME)

Despite numerous instrumental achievements, canines are still considered the most effective field method for explosive detection. However, due to strict explosive regulations and safety requirements, it can be a challenge for agencies with "bomb dogs" to train using neat explosive materials. This establishes a need for non-explosive canine training aids with the same volatile component profiles as the explosives that they represent. In order to compare mimic materials to their explosive counterparts, a technique must be established that not only allows for identification of volatile compounds but also can monitor changes in the headspace profile over time with respect to time and temperature. The Automated Training Aid Simulation using SPME (or ATASS) was developed for that purpose. As described, ATASS was used to observe changes in the volatile profile of three explosives (Composition C-4, 2,4-dinitrotoluene (DNT), and triacetone triperoxide (TATP)) and respective prototype training materials (0.1% by mass C-4, 1% by mass 2,4-DNT, and 1% by mass TATP). Samples were prepared in vials and metal tins within a gallon (≈ 3785 mL) paint can to simulate common field techniques for canine training. Monitoring these materials in real time provides a better understanding of the major volatile components present and how the relative abundances of these components can change over time. The results presented indicate that ATASS successfully allows for a sufficient comparison between explosive and non-explosive training materials.     

Real-time polymerase chain reaction quantification of canine DNA

The accurate quantification of target DNA is an important step in the short tandem repeat analysis of forensic biological samples. By utilizing quantification data to control the amount of template DNA in the polymerase chain reaction (PCR), forensic scientists can optimize testing and minimize the consumption of limited samples. The ability to identify and quantify target DNA in mixed-species samples is crucial when it may be overwhelmed by nontarget DNA, as in cases of dog attack. We evaluated two quantitative real-time PCR assays for dynamic range, species specificity, and inhibition by humic acid. While both assays proved to be highly sensitive and discriminating, the Melanocortin-1 Receptor (MC1R) gene Taqman assay had the advantages of a shorter run time, greater efficiency, and safer reagents. In its application to forensic casework, the MC1R assay has been advantageous for quantifying dog DNA in a variety of mixed-species samples and facilitating the successful profiling of individual dogs.     

Trends in explosive contamination

This study sought to assign a rough order of magnitude for the amount of explosive residue likely to be available in real-world searches for clandestine explosives. A variety of explosives (TNT, TATP, HMX, AN, RDX, PETN) in various forms (powder, flake, detonating cord, plastic) were carefully weighed or cut into containers, and the amount of residue inadvertently remaining on the work area, hands, or containers was quantified. This was used to evaluate the spillage potential of each explosive. The adhesion of each explosive to a glass surface was quantified from amount of explosive adhering to the inside of a glass vial into which the explosive had been placed and then removed by vigorous tapping. In powdered form, most of the explosives--TNT, PETN, RDX, HMX, and TATP--exhibited similar spillage and adhesion to glass. However, PETN as sheet explosive and plasticized RDX (C-4), showed very little potential to contaminate surfaces, either by spillage or adhesion to glass.