Quantification and aging of the post-blast residue of TNT landmines

Post-blast residues are potential interferents to chemical detection of landmines. To assess the potential problem related to 2,4,6-trinitrotoluene (TNT), its post-blast residue was identified and quantified. In the first part of this study laboratory-scale samples of TNT (2 g) were detonated in a small-scale explosivity device (SSED) to evaluate the explosive power and collect post-blast residue for chemical analysis. Initiator size was large relative to the TNT charge; thus, issues arose regarding choice of initiator, residue from the initiator, and afterburning of TNT. The second part of this study detonated 75 to 150 g of military-grade TNT (typical of antipersonnel mines) in 55-gal barrels containing various witness materials (metal plates, sand, barrel walls, the atmosphere). The witness materials were analyzed for explosive residue. In a third set of tests, 75-g samples of TNT were detonated over soil (from Fort Leonard Wood or Sandia National Laboratory) in an indoor firing chamber (100 by 4.6 by 2.7 m high). Targeted in these studies were TNT and four explosive-related compounds (ERC): 2,4-dinitrotoluene (DNT), 1,3-dinitrobenzene (DNB), 2- and 4-aminodinitrotoluene (2-ADNT and 4-ADNT). The latter two are microbial degradation products of TNT. Post-blast residue was allowed to age in the soils as a function of moisture contents (5 and 10%) in order to quantify the rate of degradation of the principal residues (TNT, DNT, and DNB) and formation of the TNT microbial degradation products (2-ADNT and 4-ADNT). The major distinction between landmine leakage and post-blast residue was not the identity of the species but relative ratios of amounts. In landmine leakage the DNT/TNT ratio was usually greater than 1. In post-blast residue it was on the order of 1 to 1/100th of a percent, and the total amount of pre-blast residue (landmine leakage) was a factor of 1/100 to 1/1000 less than post-blast. In addition, landmine leakage resulted in low DNT/ADNT ratios, usually less than 1, whereas pre-blast residues started with ratios above 20. Because with time DNT decreased and ADNT increased, over a month the ratio decreased by a factor of 2. The rate of TNT degradation in soil observed in this study was much slower than that reported when initial concentrations of TNT were lower. Degradation rates yielded half-lives of 40 and 100 days for 2,4-DNT and TNT, respectively.     

Particle characteristics of trace high explosives: RDX and PETN

The sizes of explosives particles in fingerprint residues produced from C-4 and Semtex-1A were investigated with respect to a fragmentation model. Particles produced by crushing crystals of RDX and PETN were sized by using scanning electron microscopy, combined with image analysis, and polarized light microscopy was used for imaging and identifying explosive particles in fingerprint residues. Crystals of RDX and PETN fragment in a manner that concentrates mass in the largest particles of the population, which is common for a fragmentation process. Based on the fingerprints studied, the particle size to target for improving mass detection in fingerprint residues by ion mobility spectrometry (IMS) is > or = 10 microm in diameter. Although particles smaller than 10 microm in diameter have a higher frequency, they constitute < 20% of the total mass. Efforts to improve collection efficiency of explosives particles for detection by IMS, or other techniques, must take into consideration that the mass may be concentrated in a relatively few particles that may not be homogeneously distributed over the fingerprint area. These results are based on plastic-bonded explosives such as C-4 that contain relatively large crystals of explosive, where fragmentation is the main process leading to the presence of particles in the fingerprint residues.     

Estimation of explosive charge mass used for explosions on concrete surface for the forensic purpose

The method of choice used by most terrorists for achieving political goals remains the utilization of explosive devices and there is always visible evidence at a crime scene after the deployment of such devices. Given favorable circumstances, forensic analysis can determine the cause of the explosion — the type of the explosive device, the means of detonation, the type and mass of the explosive charge that has been used and perhaps provide information to lead to the identity of the individual who may have constructed or deployed the explosive device, etc. Evidence of an explosion may take the form of a crater or other damage which may provide some information facilitating and estimating the mass of explosive material used. This paper reports the findings obtained by performing experimental explosions of known charges on a concrete surface, in order to establish the correlation between the charge weight and the effects of the explosion. Known masses of explosives were fired and the dimensions of craters made by explosions were measured. Five empirical equations for estimation of the explosive charge mass from crater dimensions were used.     

Application of LC−QTOF/MS for the validation and determination of organic explosive residues on Ionscan® swabs

The identification and confirmation of trace explosive residues along with potential precursors and degradation products require a comprehensive laboratory analysis procedure. This study presents the determination of organic explosives consisting of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2,4,6,N-tetranitro-N-methylaniline (Tetryl), 1,3,5-trinitrobenzene (1,3,5-TNB) and pentaerythritol tetranitrate (PETN) by a high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC−QTOF/MS). The qualitative information including retention time, collision energy, precursor ions, and characteristic fragmentation pattern of each explosive were collected using an atmospheric pressure chemical ionization (APCI) in negative ion mode. The separation efficiency among five compounds was greatly achieved in this study. Four real explosive samples consisting of TNT, RDX, PETN and Tetryl and 12 Ionscan® quality control swabs from the Royal Thai Army were also tested to validate and verify the viability of the GC–MS method used to validate results from an Ionscan® system. The results showed that LC−QTOF/MS is a powerful technique for the identification and confirmation of thermally unstable organic explosives on Ionscan® swabs compared to a conventional GC−MS technique.     

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.     

The Anatomy of a Pipe Bomb Explosion: Measuring the Mass and Velocity Distributions of Container Fragments

Improvised explosive devices such as pipe bombs are prevalent due to the availability of materials and ease of construction. However, little is known about how these devices actually explode, as few attempts to characterize fragmentation patterns have been attempted. In this study, seven devices composed of various pipe materials (PVC, black steel, and galvanized steel) and two energetic fillers (Pyrodex and Alliant Red Dot) were initiated and the explosions captured using high‐speed videography. The video footage was used to calculate fragment velocities, which were represented as particle velocity vector maps. In addition, the fragments were weighed. The results demonstrate a correlation between the type of energetic filler and both the size and velocity of the fragments. Larger fragments were produced by Pyrodex filler indicating a less complete fragmentation, compared with smaller fragments produced by double‐base smokeless powder. Additionally, higher fragment velocities were seen with Alliant Red Dot filler.     

LC-ESI-MS/MS法分析爆炸尘土中的硝化甘油

目的建立了高效液相色谱-质谱/质谱法（LC-ESI-MS/MS）测定尘土中的硝化甘油（NG）的方法,为日后测定爆炸残留物中的NG奠定基础。方法采用液液提取的方式提取样品,考察了前处理条件、色谱条件及质谱参数,最终确定实验方法。结果选择了最佳液相色谱质谱分析方法：固定相为SB C18（4.6×150 mm,5μm）,甲醇—0.05 mmol氯化铵做流动相,甲醇作提取溶剂;该方法在0.25～10 ng/g范围内呈良好线性,相关系数为0.9990;定量下限为0.25 ng/g;加标回收率为90.4%～95.2%。结论本方法操作简单,提取方便,有效避免了尘土复杂基质的干扰,结果准确可靠,灵敏度高,满足对爆炸残留物中硝化甘油的检测要求。     

Determination of elemental sulfur in explosives and explosive residues by gas chromatography-mass spectrometry

A new method for the positive identification of elemental sulfur in explosives and explosive residues is developed. Following a carbon disulfide wash of explosives or explosive residues, a sample of the extracted material is injected onto a gas chromatography (GC) column, then analyzed via mass-selective (MS) detection. A positive identification of elemental sulfur is based on both retention time and fragmentation pattern. The GC-MS method is demonstrated to be useful in detecting and positively identifying elemental sulfur from both burned and unburned explosive mixtures. With a detection limit of 2.5 ng (2.5 x 10(-9) grams) of elemental sulfur on the column, it is shown to be 400 times more sensitive than the presumptive chemical color test that is currently the method employed for detection of small amounts of sulfur.     

Quantified Explosives Transfer on Surfaces for the Evaluation of Trace Detection Equipment

Trace explosive test surfaces are often required for the evaluation of trace detection equipment to determine the equipment performance. Test surfaces of C‐4, Detasheet, Semtex‐H, TNT, and HMTD were prepared by transferring trace amount of explosive deposited on polytetrafluoroethylene (PTFE) transfer strips onto different surfaces (Kraft paper, hard plastic, woven fabric, and soft vinyl). The amount of explosive transferred was deduced from the amount of explosive remaining on the PTFE strips after transfer, as quantified by direct analysis using tandem mass spectrometry with thermal desorption. From the data set of over 2000 transfers, we experienced lower transfer efficiency for Semtex‐H and Detasheet, and for soft vinyl and hard plastic. However, the rapid quantification mass spectrometric method allowed the transfer efficiency to be determined for all test surfaces used in an evaluation of trace explosive detectors, thereby permitting only the test surfaces with desired transfer to be accepted for the assessment.     

Screening and elucidation of fragmentations of 23 diuretics in dietary supplements using UHPLC-Q-Orbitrap

Diuretics are used to treat the edematous state in cases of renal insufficiency, nephrotic syndrome, liver cirrhosis, and heart failure. These compounds are used by athletes to lose weight and are included in the list of prohibited substances by the World Anti-Doping Agency. They are also used by obese and overweight people for losing weight, and there are a number of recent reports on the contamination of dietary supplements with diuretics. Due to the alluring online marketing and blogging, there is an extensive misuse of products that are illegally adulterated with diuretics, which has seriously increased health risks. Therefore, it is essential to develop an analytical method for the detection of adulterants in such substances. In this study, 23 diuretics, categorized into four groups, namely, thiazide diuretics (e.g., bendroflumethiazide), loop diuretics (e.g., bumetanide), potassium-sparing diuretics (e.g., amiloride), and carbonic anhydrase inhibitors (e.g., acetazolamide), were analyzed using ultrahigh-performance liquid chromatography-quadrupole orbitrap (UHPLC-Q-Orbitrap). Their fragmentation was elucidated based on the MS/MS data. The 124 products were screened by the UHPLC-Q-Orbitrap (LC-HRMS) method, and the confirmed compounds were quantitated by a previously established LC-MS/MS method. Approximately 5% of the samples were found to be illegally contaminated with diuretics at a concentration of 0.051–162 mg/g. The high selectivity and sensitivity of the UHPLC-Q-Orbitrap (LC-HRMS) method, in combination with the established fragmentation, offer a new approach for the rapid and accurate screening of diuretics in adulterated products, which would be ultimately beneficial for the public health.     

涉爆案件中烟火剂的检验

目的　建立涉爆案件中烟火剂的快速、准确的检验方法。方法　以扫描电镜 /能谱仪分析为主 ,红外光谱分析为辅 ,对爆炸装置尤其爆炸残留物中的烟火剂进行形态和成分分析。结果　对烟火剂原体的检验快速、准确 ,通过比对分析可确定烟火剂的来源 ,对爆炸残留物中的烟火剂进行准确定性。结论　该方法对各种检材中的烟火剂检验稳定性好、准确率高 ,且操作简便 ,具有很强的实用性     

Analysis of explosive damage in metals using orientation imaging microscopy

The goal of this project was to determine whether quantitative information concerning the size and nature of an explosive blast could be determined using Orientation Imaging Microscopy (OIM) to analyze the texture of blast-affected metal. Selected 1018 steel and 2024 aluminum samples were subjected to various explosive blasts chosen to simulate a wide range of possible pressure waves. The explosives used were PBX 9404, Comp-C4, Gelmax, and Bullseye. The explosive tests were carried out at Sandia National Laboratory, and the OIM analysis was conducted at Ames Laboratory. It was discovered that while suitable patterns could be obtained from the steel samples, the oxide layer present on the surface of the aluminum samples prevented these samples from being studied. The results of the OIM studies on the steel samples indicate that damage can be tracked using OIM imaging and that Comp-C4 seems to produce patterns significantly different than the other explosives.     

Detecting file fragmentation point using sequential hypothesis testing

File carving is a technique whereby data files are extracted from a digital device without the assistance of file tables or other disk meta-data. One of the primary challenges in file carving can be found in attempting to recover files that are fragmented. In this paper, we show how detecting the point of fragmentation of a file can benefit fragmented file recovery. We then present a sequential hypothesis testing procedure to identify the fragmentation point of a file by sequentially comparing adjacent pairs of blocks from the starting block of a file until the fragmentation point is reached. By utilizing serial analysis we are able to minimize the errors in detecting the fragmentation points. The performance results obtained from the fragmented test-sets of DFRWS 2006 and 2007 show that the method can be effectively used in recovery of fragmented files.     

Detecting file fragmentation point using sequential hypothesis testing

File carving is a technique whereby data files are extracted from a digital device without the assistance of file tables or other disk meta-data. One of the primary challenges in file carving can be found in attempting to recover files that are fragmented. In this paper, we show how detecting the point of fragmentation of a file can benefit fragmented file recovery. We then present a sequential hypothesis testing procedure to identify the fragmentation point of a file by sequentially comparing adjacent pairs of blocks from the starting block of a file until the fragmentation point is reached. By utilizing serial analysis we are able to minimize the errors in detecting the fragmentation points. The performance results obtained from the fragmented test-sets of DFRWS 2006 and 2007 show that the method can be effectively used in recovery of fragmented files.     

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.     

Evaluation of different sampling media for their potential use as a combined swab for the collection of both organic and inorganic explosive residues

Commercially available skin cleansing alcohol wipes and conventional swabs were investigated for their use as a universal sampling medium for the simultaneous collection of both organic and inorganic explosive residues. Six compounds with the potential to be encountered in casework [pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), triacetone triperoxide (TATP), ammonium nitrate, and sodium chlorate] were selected as representative target compounds. Quantities of these target compounds were deposited on four different substrates (glass, plastic, aluminium foil and laminate). Two chosen alcohol wipes demonstrated better overall performance in the recovery of both the organic and inorganic representative compounds from each of the test surfaces compared to the results obtained using conventional cotton and polyester swabs, pre-moistened with various solvents, and a direct methanol wash (used as a control). Results obtained using dry cotton swabs indicated that it was not an effective swabbing system for the collection of both organic and inorganic explosive residues on common substrates.     

The use of capillary electrophoresis in the detection of monomethylamine and benzoate ions in the forensic examination of explosives residues

Capillary electrophoresis (CE) is used in the ATF Forensic Science Laboratories for the analysis of inorganic ions commonly encountered in post-blast residues including monomethylamine (MMA) and benzoate ions. Monomethylamine nitrate is found in Tovex, a water gel explosive. Sodium benzoate is added to Pyrodex, as a fuel and burn rate modifier. In the analysis of explosive residues, these ions are used as an indicator for the presence of Tovex and Pyrodex. Traditionally, these two ions, along with other ions of interest were analyzed by spot tests and ion chromatograph (IC). CE is currently being used in place of spot tests as a confirmation technique for IC.     

Surface-sampling and analysis of TATP by swabbing and gas chromatography/mass spectrometry

The method of sample recovery for trace detection and identification of explosives plays a critical role in several criminal investigations. After bombing, there can be difficulties in sending big objects to a laboratory for analysis. Traces can also be searched for on large surfaces, on hands of suspects or on surfaces where the explosive was placed during preparatory phases (e.g. places where an IED was assembled, vehicles used for transportation, etc.).In this work, triacetone triperoxide (TATP) was synthesized from commercial precursors following reported methods. Several portions of about 6 mg of TATP were then spread on different surfaces (e.g. floors, tables, etc.) or used in handling tests. Three different swabbing systems were used: a commercial swab, pre-wetted with propan-2-ol (isopropanol) and water (7:3), dry paper swabs, and cotton swabs wetted with propan-2-ol. Paper and commercial swabs were also used to sample a metal plate, where a small charge of about 4 g of TATP was detonated. Swabs were sealed in small glass jars with screw caps and Parafilm^® M and sent to the laboratory for analysis. Swabs were extracted and analysed several weeks later by gas chromatography/mass spectrometry. All the three systems gave positive results, but wetted swabs collected higher amounts of TATP. The developed procedure showed its suitability for use in real cases, allowing TATP detection in several simulations, including a situation in which people wash their hands after handling the explosive.     

Accumulation of explosives in hair--part II: factors affecting sorption

This study examines the sorption of eight explosives (2,4,6-trinitrotoluene [TNT]; pentaerythritol tetranitrate [PETN]; hexahydro-1,3,5-trinitro-s-triazine [RDX]; diacetone diperoxide [DADP]; triacetone triperoxide [TATP]; ethylene glycol [EGDN], nitroglycerin [NG]; and 2,4-dinitrotoluene [DNT]) to human hair. The study uses only cut hair, which is exposed to explosive vapor. The vapor transfer studies reported herein indicated that hair did not reach saturation even after 2.5 years of exposure to TNT. While previous studies showed black hair sorbed more explosive than blond or brown, this study reports that red hair sorption is similar to black, while grey hairs, exposed along with black hair from the same individual, sorbed significantly less explosive than the same individual's black hairs. In a study using only black hair, a slight racial bias was observed with sorption greater for Mongoloid hair as compared to Caucasian or Negroid. Only for Mongoloid hairs were enough samples studied to examine for a gender bias, but one was not observed. There was much variability in results in all categories (hair color, race, and gender) that trends were established only in general terms. Hair at different ages was tested for a few individuals. Detailed studies focused on the sorption of TATP and TNT as these appear to be sorbed most differently-TATP mainly on the hair surface and TNT both on the surface and in the cortex. The uptake of high vapor pressure explosives (e.g., TATP) and moderate vapor pressure explosives (e.g., TNT) by hair was rapid and could be detected within about 1 h of exposure. Both explosives were readily sorbed by pure melanin.     

Linking ammonium nitrate-aluminum (AN-AL) post-blast residues to pre-blast explosive materials using isotope ratio and trace elemental analysis for source attribution

Forensic science practitioners are often called upon to attribute crimes using trace evidence, such as explosive remnants, with the ultimate goal of associating a crime with a suspect or suspects in order to prevent further attacks. The explosive charge is an attractive component for attribution in crimes involving explosives as there are limited pathways for acquisition. However, there is currently no capability to link an explosive charge to its source via post-blast trace residues using isotope ratios or trace elements. Here, we sought to determine if pre-blast attribution signatures are preserved after detonation and can be subsequently recovered and detected. A field study was conducted to recover samples of post-blast explosives from controlled detonations of ammonium nitrate-aluminum (AN-Al), which were then analyzed via isotope ratio mass spectrometry (IRMS) and inductively coupled plasma-mass spectrometry (ICP-MS) for quantitation and profiling of isotopes ratio and trace element signatures, respectively. Oxygen and nitrogen isotope ratios from AN-Al yielded some of the most promising results with considerable overlap within one standard deviation of the reference between the spreads of pre- and post-blast data. Trace element results from AN-Al support the findings in the isotope ratio data, with 26 elements detected in both pre- and post-blast samples, and several elements including B, Cd, Cr, Ni, Sn, V, and Zn showing considerable overlap. These preliminary results provide a proof-of-concept for the development of forensic examinations that can attribute signatures from post-blast debris to signatures in pre-blast explosive materials for use in future investigations.