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.

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.