Chemical attribution of the homemade explosive ETN - Part II: Isotope ratio mass spectrometry analysis of ETN and its precursors.

In this follow-up study the collaboration between two research groups from the USA and the Netherlands was continued to expand the framework of chemical attribution for the homemade explosive erythritol tetranitrate (ETN). Isotope ratio mass spectrometry (IRMS) analysis was performed to predict possible links between ETN samples and its precursors. Carbon, nitrogen, hydrogen and oxygen isotope ratios were determined for a wide variety of precursor sources and for ETN samples that were prepared with selected precursors. The stability of isotope ratios of ETN has been demonstrated for melt-cast samples and two-year old samples, which enables sample comparison of ETN in forensic casework independent of age and appearance. Erythritol and nitric acid (or nitrate salt) are the exclusive donor of carbon and nitrogen atoms in ETN, respectively, and robust linear relationships between precursor and the end-product were observed for these isotopes. This allowed for defining isotopic enrichment ranges for carbon and nitrogen that support the hypothesis that a given erythritol or nitrate precursor was used to synthesize a specific ETN batch. The hydrogen and oxygen atoms in ETN do not originate from one exclusive donor material, making linkage prediction more difficult. However, the large negative enrichments observed for both isotopes do provide powerful information to exclude suspected precursor materials as donor of ETN. Additionally, combing the isotopic data of all elements results in a higher discrimination power for ETN samples and its precursor materials. Combining the findings of our previously reported LC-MS analysis of ETN with this IRMS study is expected to increase the robustness of the forensic comparison even further. The partially nitrated impurities can provide insight on the synthesis conditions while the isotope data contain information on the raw materials used for the production of ETN.

Emerging techniques for the detection of pyrotechnic residues from seized postal packages containing fireworks.

High volume screening of parcels with the aim to trace the illegal distribution and selling of fireworks using postal services is challenging. Inspection services have limited manpower and means to perform extensive visual inspection. In this study, the presence of solid pyrotechnic residues collected from cardboard shipping parcels containing fireworks was investigated for direct in-field chemical detection. Two emerging trace detection techniques, i.e., capillary electrophoresis (CE)-based inorganic oxidizer detector and infrared thermal desorption (IRTD) coupled with direct analysis in real time mass spectrometry (DART-MS), were investigated for their potential as screening tools. Detection of non-visible pyrotechnic trace residues from real-case seized parcels was demonstrated using both screening techniques. However, the high nitrate background in the commercial CE system complicated its screening for black powder traces. IRTD-DART-MS allowed differentiation between flash and black powder by identification of the molecular inorganic ions. Compared to the portable CE instrument, rapid screening using IRTD-DART-MS is currently limited to laboratory settings. The capabilities of these emerging techniques established solid particle and trace residue chemical detection as interesting options for parcel screening in a logistic setting.

Chemical attribution of the home-made explosive ETN - Part I: Liquid chromatography-mass spectrometry analysis of partially nitrated erythritol impurities.

Erythritol tetranitrate (ETN) was prepared independently by two research groups from the USA and the Netherlands. The partially nitrated impurities present in ETN were studied using liquid chromatography-mass spectrometry to address the ultimate challenge in forensic explosives investigations, i.e., providing chemical and tactical information on the production and origin of the explosive material found at a crime scene. Accurate quantification of the tri-nitrated byproduct erythritol trinitrate (ETriN) was achieved by in-lab production of an ETriN standard and using custom-made standards of the two isomers of ETriN (1,2,3-ETriN and 1,2,4-ETriN). Large differences in levels of ETriN were observed between the two sample sets showing that, even when similar synthesis routes are employed, batches from different production locations can contain different impurity profiles. In one of the sample sets the ratios of the lesser partially nitrated impurities, EDiN and EMN, in the ETN samples could be determined. The impurity profiles enable prediction of post-synthesis work-up steps by reduction of the level of partially nitrated products upon recrystallization. However, impurity analysis does not enable predictions with respect to raw material or synthesis route used. Nonetheless, characteristic impurity profiles obtained can be used in forensic casework to differentiate or link ETN samples. However, forensic interpretation can be complicated by acid catalyzed degradation which can cause changes in impurity levels over time. The high food-grade quality of the erythritol precursor materials did not provide other impurity markers using the LC-MS methods in this study. To expand our framework of chemical attribution a follow-up study will be reported that focuses on stable isotope analysis of ETN and its precursor materials that potentially allow predictions for forensic explosives intelligence.

Multicomponent characterization and differentiation of flash bangers - Part II: Elemental profiling of plastic caps.

This study builds on the multicomponent analysis strategy for flash bangers which was previously introduced and where a representative sample set has been collected of a certain type of flash bangers. To expand the forensic strategy, elemental analysis of the plastic caps which are present in these items was performed. Both x-ray fluorescence (XRF) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis was performed to explore the possibilities for differentiation. The inherent inhomogeneity of the plastics resulted in high variations, especially for LA-ICP-MS trace analysis. In addition, due to the lack of suitable reference materials the LA-ICP-MS results can only be used for qualitative comparisons. Although XRF is less sensitive it allows for semi-quantitative analysis and the effect of inhomogeneity is significantly reduced due to the larger sample areas. Therefore, XRF is the method of choice for elemental analysis of intact plastic caps. In this scenario initial differentiation based on visual examination is combined with elemental analysis to obtain the highest degree of discrimination. In post-explosive scenarios, using XRF is not as straightforward due the irregular shapes of the burned plastic cap residues and contamination by explosive residues. For the analysis of these post-explosive caps, LA-ICP-MS proved to be useful for characterization and differentiation. Overall, it was found that blue caps contain a considerable higher amount of elements than the white caps, mainly due to additives related to the coloring process. This limits differentiation for the flash bangers containing white caps. Therefore, isotope ratio mass spectrometry (IRMS) analysis was performed to increase the differentiation potential. Based on carbon and hydrogen isotope ratios additional sets could be distinguished, both for flash bangers containing white and blue caps, that otherwise have similar visual and elemental characteristics. With the elemental and isotopic analysis of the plastic caps, an analysis strategy has been introduced that is not based on the pyrotechnic charge and therefore provides a unique opportunity to perform characterization and differentiation of flash bangers in pre- and post-explosive casework.

Multicomponent characterization and differentiation of flash bangers - Part I: Sample collection and visual examination.

To continue to assist law enforcement agencies in counteracting the illegal use of fireworks new forensic methods have to be developed. In the Netherlands, many incidents involve powerful flash bangers mainly due to irresponsible behavior and misuse for criminal activities. Obtaining tactical information for differentiation of these flash bangers is of high priority in forensic casework. A representative sample set of a certain type of flash bangers, confiscated by the Dutch police, has been collected in a time period of one year and initial characterization has been performed based on visual examination. The individual components of the flash bangers already allow for a high degree of differentiation. Ultimately, combining all visual characteristics of pyrotechnic charges, labels, fuses and caps resulted in the classification into 24 groups out of 30 seized sets of flash bangers. In addition to visual examination, this unique sample set offers a wide variety of research opportunities that could be further explored and that might prove essential in case scenarios where visual characteristics are more difficult to assess or are completely absent.

Analysis of Urine, Oral fluid and Fingerprints by Liquid Extraction Surface Analysis Coupled to High Resolution MS and MS/MS - Opportunities for Forensic and Biomedical Science.

Liquid Extraction Surface Analysis (LESA) is a new, high throughput tool for ambient mass spectrometry. A solvent droplet is deposited from a pipette tip onto a surface and maintains contact with both the surface and the pipette tip for a few seconds before being re-aspirated. The technique is particularly suited to the analysis of trace materials on surfaces due to its high sensitivity and low volume of sample removal. In this work, we assess the suitability of LESA for obtaining detailed chemical profiles of fingerprints, oral fluid and urine, which may be used in future for rapid medical diagnostics or metabolomics studies. We further show how LESA can be used to detect illicit drugs and their metabolites in urine, oral fluid and fingerprints. This makes LESA a potentially useful tool in the growing field of fingerprint chemical analysis, which is relevant not only to forensics but also to medical diagnostics. Finally, we show how LESA can be used to detect the explosive material RDX in contaminated artificial fingermarks.

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 (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), 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.

Isotopic and elemental profiling of ammonium nitrate in forensic explosives investigations.

Ammonium nitrate (AN) is frequently encountered in explosives in forensic casework. It is widely available as fertilizer and easy to implement in explosive devices, for example by mixing it with a fuel. Forensic profiling methods to determine whether material found on a crime scene and material retrieved from a suspect arise from the same source are becoming increasingly important. In this work, we have explored the possibility of using isotopic and elemental profiling to discriminate between different batches of AN. Variations within a production batch, between different batches from the same manufacturer, and between batches from different manufacturers were studied using a total of 103 samples from 19 different fertilizer manufacturers. Isotope-ratio mass spectrometry (IRMS) was used to analyze AN samples for their (15)N and (18)O isotopic composition. The trace-elemental composition of these samples was studied using inductively coupled plasma-mass spectrometry (ICP-MS). All samples were analyzed for the occurrence of 66 elements. 32 of these elements were useful for the differentiation of AN samples. These include magnesium (Mg), calcium (Ca), iron (Fe) and strontium (Sr). Samples with a similar elemental profile may be differentiated based on their isotopic composition. Linear discriminant analysis (LDA) was used to calculate likelihood ratios and demonstrated the power of combining elemental and isotopic profiling for discrimination between different sources of AN.

Impurity profiling of trinitrotoluene using vacuum-outlet gas chromatography-mass spectrometry.

In this work, a reliable and robust vacuum-outlet gas chromatography-mass spectrometry (GC-MS) method is introduced for the identification and quantification of impurities in trinitrotoluene (TNT). Vacuum-outlet GC-MS allows for short analysis times; the analysis of impurities in TNT was performed in 4min. This study shows that impurity profiling of TNT can be used to investigate relations between TNT samples encountered in forensic casework. A wide variety of TNT samples were analyzed with the developed method. Dinitrobenzene, dinitrotoluene, trinitrotoluene and amino-dinitrotoluene isomers were detected at very low levels (<1wt.%) by applying the MS in selected-ion monitoring (SIM) mode. Limits of detection ranged from 6ng/mL for 2,6-dinitrotoluene to 43ng/mL for 4-amino-2,6-dinitrotoluene. Major impurities in TNT were 2,4-dinitrotoluene and 2,3,4-trinitrotoluene. Impurity profiles based on seven compounds showed to be useful to TNT samples from different sources. Statistical analysis of these impurity profiles using likelihood ratios demonstrated the potential to investigate whether two questioned TNT samples encountered in forensic casework are from the same source.

Accurate quantitation of pentaerythritol tetranitrate and its degradation products using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

After an explosion of pentaerythritol tetranitrate (PETN), its degradation products pentaerythritol trinitrate (PETriN), dinitrate (PEDiN) and mononitrate (PEMN) were detected using liquid chromatography-atmospheric-pressure chemical-ionization-mass spectrometry (LC-APCI-MS). Discrimination between post-explosion and naturally degraded PETN could be achieved based on the relative amounts of the degradation products. This information can be used as evidence when investigating a possible relationship between a suspect and a post-explosion crime scene. The present work focuses on accurate quantitation of PETN and its degradation products, using PETriN, PEDiN and PEMN standards specifically synthesized for this purpose. With the use of these standards, the ionization behavior of these compounds was studied, and a quantitative method was developed. Quantitation of PETN and trace levels of its degradation products was shown to be possible with accuracy between 85.7% and 103.7% and a precision ranging from 1.3% to 11.5%. The custom-made standards resulted in a more robust and reliable method to discriminate between post-explosion and naturally-degraded PETN.

Development and validation of highly selective screening and confirmatory methods for the qualitative forensic analysis of organic explosive compounds with high performance liquid chromatography coupled with (photodiode array and) LTQ ion trap/Orbitrap mass spectrometric detections (HPLC-(PDA)-LTQOrbitrap).

An LTQ-Orbitrap FTMS is a new (hybrid) mass spectrometric (MS) analyzer. It allows for the acquisition of full scan MS(n) (n-stage fragmentations, n=1-n) spectra with the linear ion trap detector (LTQ) at high speed and/or with the Fourier Transform-detector (Orbitrap) with ultra high mass resolution (>60,000 at m/z<400amu) and high mass accuracy (≤1ppm with internal calibration). In addition it may be coupled with liquid chromatography (LC) with photo diode array (PDA) detection. Two methods for the forensic screening and confirmation of all common trace explosives in post-blast residues have been developed on this instrument using atmospheric pressure chemical ionization (APCI). In one run, the nitrogen-containing explosives are analyzed with the combination of "LC-(PDA)-APCI(-)-LTQ MS(2)/Orbitrap FTMS" (Method 1). In another run, peroxide explosives are analyzed with "LC-APCI(+)-LTQ MS(2)/Orbitrap FTMS" (Method 2). The performance of both methods has been validated according to procedures defined in the EU COMMISSION DECISION implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results (DC 2002/657/EC) and other standards (NEN 17025 and NEN 7777). The methods are highly selective due to the simultaneous utilization of the Orbitrap FTMS and LTQ MS(2), both of which are highly selective detectors Tested explosive compounds can be detected in the molecular ion form by the Orbitrap analyzer with minimal mass interference in different matrices when using an extremely narrow mass tolerance detection window (≤2ppm). The identification of a detected compound follows an identification point system. Experimental results show that almost all explosive compounds meet the confirmation criteria (minimum 4 points) required for the positive identification by the DC 2002/657/EC.

Pentaerythritol tetranitrate (PETN) profiling in post-explosion residues to constitute evidence of crime-scene presence.

Pentaerythritol tetranitrate (PETN) and its degradation products are analyzed to discriminate between residues originating from PETN explosions and residues obtained under other circumstances, such as natural degradation on textile, or after handling intact PETN. The degradation products observed in post-explosion samples were identified using liquid chromatography-mass spectrometry as the less-nitrated analogues of PETN: pentaerythritol trinitrate (PETriN), pentaerythritol dinitrate (PEDiN) and pentaerythritol mononitrate (PEMN). Significant levels of these degradation products were observed in post-explosion samples, whereas only very low levels were detected in a variety of intact PETN samples and naturally degraded PETN. No significant degradation was observed after 12 weeks of storage at room temperature and the influence of high relative humidity (90%) was found to be small. Natural degradation was accelerated by storage of small amounts of PETN on different types of textile, resembling the clothing of a suspect, at elevated temperature (333K). This resulted in significant levels of PETN degradation products, but the relative amounts remained much lower than in post-explosion PETN. For PETriN the peak area relative to PETN was 0.014 (SD=0.0051) and 0.39 (SD=0.19) respectively. Based on the peak areas of PETriN, PEDiN and PEMN relative to PETN, it was possible to fully distinguish the post-explosion profiles from the profiles obtained from intact PETN or after (accelerated) natural degradation. Although more data are required to accurately assess the strength of the evidence, this work illustrates that PETN profiling may yield valuable evidence when investigating a possible link between a suspect and post-explosion PETN found on a crime scene. Due to the substantial variation in the degradation pattern between explosion experiments and even between sampling positions in one experiment, the method is not able to distinguish different PETN explosion events.

Investigation of isotopic linkages between precursor materials and the improvised high explosive product hexamethylene triperoxide diamine.

The results of isotope ratio mass spectrometry (IRMS) on hexamethylene triperoxide diamine (HMTD) and its precursor hexamethylenetetramine (hexamine) is presented. HMTD was prepared from hexamine using several different sources of hexamine under both controlled laboratory conditions and in field experiments that represent the less controlled conditions that are likely to be observed in forensic casework scenarios. Precursor and product carbon isotope δ values consistently fit a linear relationship regardless of precursor or conditions. The magnitude of the isotope fractionation observed is affected by the efficiency of the reaction, with greater yielding reactions giving rise to HMTD with δ values more similar to the precursor material than lower yielding reactions. Nitrogen isotope δ values comparing precursor with product show some linearity when the reaction conditions are carefully controlled; however, results indicate a poor fit with linearity when synthesis conditions are more variable. Despite the greater variation, the HMTD product consistently has a more positive δ value compared with the hexamine precursor. The results observed from these experiments suggest hexamine reacts to form HMTD in a 1:1 ratio. Having prepared multiple HMTD samples from various precursors using a range of experimental conditions, we have observed results that may be useful in forensic investigations of improvised explosive materials.

Morphology and composition of pyrotechnic residues formed at different levels of confinement.

Post explosion residues (PER) are residues from pyrotechnic compositions or explosives that are generated during an explosion. In the recent past SEM/EDX was used several times to analyze PER from pyrotechnic compositions. The results from these studies suggest that there might be a difference in morphology and composition of pyrotechnic residues formed at different levels of confinement. Also because of general thermodynamic principles it is believed that at higher levels of confinement the final pressure and temperature during the explosion is probably (but not necessarily) higher, eventually resulting in smaller and more spherical particles and a more homogeneous elemental composition. If there is a relation between morphology and composition of pyrotechnic residues and the level of confinement at which these are formed, it would be possible to draw conclusions about the conditions at which pyrotechnic residues were formed and the kind and construction of the device used. This may aid forensic scientists not only in the determination of the original explosive composition, but also of the explosive device. To perform controlled experiments with pyrotechnic charges at, at least, two pre-set levels of confinement a test vessel was built by TNO Defence, Security and Safety. For this study, three different flash powder compositions and black powder were selected. The generated residues were sampled on collecting plates and Nucleopore filters connected to a pump system in the immediate vicinity of the venting area for further analyses by SEM/EDX and XRD. From the results it follows that in the pressure range studied, the level of confinement seems to have a minor effect on the features of the generated residue particles. Because passive sampling by means of collector plates seemed doubtful and because the number of experiments had to be limited it is impossible to draw definitive conclusions. In addition to the level of confinement several other variables may affect size, shape and composition of pyrotechnic residues. More experiments and improved sampling methods are necessary to determine what variables have the most pronounced effect on shape size and composition of pyrotechnic residues.

High-frequency dielectric relaxation of liquid crystals: THz time-domain spectroscopy of liquid crystal colloids.

Terahertz time-domain spectroscopy has been used to study the dielectric relaxation of pure 4'-n-pentyl-4-cyanobiphenyl (5CB) liquid crystal (LC) and its mixtures with 10 mum SiO2 particles in the frequency range 0.2-2 THz. For the pure sample, we find that spatial inhomogeneities consisting of oriented domains, comparable in size to our probe area (~1 mm(2)), cause a large scatter in the measured dielectric function, due to varying contributions from the ordinary and extraordinary components. In the LC/particle mixtures, ordering of the LC at the surface of the SiO2 particles results in a break-up of these domains, giving rise to a spatially much more homogeneous dielectric response. The inferred dielectric function can be interpreted using effective medium theory and the Debye relaxation model. We observe this stabilizing effect for interparticle distances < ~30 mum, setting a lower limit for the size of oriented domains in the bulk LC.

Synthesis and properties of monodisperse oligofluorene-functionalized truxenes: highly fluorescent star-shaped architectures.

This paper describes the strategy toward novel monodisperse, well-defined, star-shaped oligofluorenes with a central truxene core and from monofluorene to quaterfluorene arms. Introduction of solubilizing n-hexyl groups at both fluorene and truxene moieties results in highly soluble, intrinsically two-dimensional nanosized macromolecules T1-T4. The radius for the largest oligomer of ca. 3.9 nm represents one of the largest known star-shaped conjugated systems. Cyclic voltammetry experiments reveal reversible or quasi-reversible oxidation and reduction processes (Eox = +0.74 to 0.80 V, Ered = -2.66 to 2.80 eV vs Fc/Fc+), demonstrating excellent electrochemical stability toward both p- and n-doping, while the band gaps of the oligomers are quite high (EgCV = 3.20-3.40 eV). Close band gaps of 3.05-3.29 eV have been estimated from the electron absorption spectra. These star-shaped macromolecules demonstrate good thermal stability (up to 400-420 degrees C) and improved glass transition temperatures with an increase in length of the oligofluorene arms (from Tg = 63 degrees C for T1 to 116 degrees C for T4) and show very efficient blue photoluminescence (lambdaPL = 398-422 nm) in both solution (PhiPL = 70-86%) and solid state (PhiPL = 43-60%). Spectroelectrochemical experiments reveal that compounds T1-T4 are stable electrochromic systems which change their color reversibly from colorless in the neutral state (approximately 340-400 nm) to colored (from red to purple color; approximately 500-600 nm) in the oxidized state.