Chemical Profiling of Ballistic Materials - Analysis of organic gunshot residue

Gunshot residue (GSR) is a complex chemical mixture that is created during the discharge of a firearm. Its detection and interpretation play a crucial role in the investigation of firearm incidents. Current GSR analysis is limited to inorganic GSR (IGSR), however, the evidential value could be strengthened by inclusion of organic GSR (OGSR). The present study aims to address this potential by proposing a categorisation system for relevant OGSR compounds and developing a methodology for the collection, extraction and analysis of both organic and inorganic GSR from a single sample. The organic composition of more than 50 propellant powders has been determined and compared against more than 200 propellant compositions reported in the literature. This work has resulted in a three-tier categorisation system for OGSR compounds, which together with the current IGSR classification will provide unequivocal identification of GSR materials with the possibility of discriminating between GSR from different ammunition types. Evaluation of MonoTrap extraction showed that this is an effective pre-concentration technique for the characterisation of propellants. Solid-phase microextraction (SPME), however, was the superior method for the extraction of OGSR compounds from various sampling media, including swabs and stubs. The optimised methodology involves GSR collection using carbon adhesive stubs followed by SPME gas chromatography – mass spectrometry (GC-MS) analysis of OGSR and subsequent scanning electron microscopy – energy-dispersive X-ray spectrometry (SEM-EDX) analysis for IGSR. This protocol has resulted in the detection of both characteristic IGSR and categorised organic compounds, demonstrating the ability to obtain a full chemical profile from a single sample. Detection of both first and second tier organic compounds provides complementary compositional information that could be used to discriminate between samples. Furthermore, this methodology requires no changes to the current sampling and IGSR analysis protocols and addresses the limited storage time of OGSR. Since GC-MS instruments are readily available in most analytical laboratories, implementation of the proposed protocol is feasible

Recent trends in organic gunshot residue analysis – a review.

A comprehensive review of the literature concerning all aspects of sampling and analytical techniques used for the determination of organic gunshot residue (OGSR) compounds is presented. Currently, 136 compounds associated with OGSR have been identified in the literature. Despite this area gaining increasing attention and recognition in recent years, there is still an absence of a set combination of sample collection, extraction and analysis methods that are universally optimal for the treatment of any given OGSR sample. Moreover, there are no generally accepted guidelines for selecting the compounds of interest that will inform sampling and analysis protocols. We highlight recent developments in both extraction and analytical methods employed for their detection. The main advantages and disadvantages of the sampling and analysis methods are critically discussed

Preliminary classification of characteristic organic gunshot residue compounds.

For the first time, a classification system for organic gunshot residue (OGSR) compounds with respect to the confirmation of OGSR materials is presented. There are 136 compounds considered to be associated with OGSR that have been highlighted in the literature. Many of these compounds could be classified as being ubiquitous in the environment and thus their detection as characteristic components of OGSR could cause issues with the interpretation of chemical ballistic evidence. The proposed system aims to address this problem by classifying OGSR compounds based on their forensic relevance with respect to the confirmation of GSR materials. To increase the forensic relevance of such a system, the large number of OGSR compounds reported in the literature has been decreased to 20 OGSR compounds based on the organic chemical composition of over 200 propellant powders. Occupational and environmental materials also associated with OGSR compounds have been considered

Organic compositional analysis of propellant powders using monolithic material sorption extraction ( MSSE) - a feasibility study

The application of monolithic material sorption extraction, specifi cally MonoTrapTM, to the extraction of organic gunshot residue (OGSR) compounds from unburnt propellant powders is described. Four different MonoTraps were assessed for their capability to extract OGSR compounds from two different ammunition types. Extracts were analysed using gas chromatography-mass spectrometry. Results indicated that the carbon disc was suitable for the extraction of OGSR compounds from unburnt propellant powders. Quantities for major compounds were comparable to methanol extractions. The method was successfully used to detect a wide range of OGSR compounds, including nitrotoluenes, nitroglycerin, diphenylamines and centralites and is expected to be applicable to a wide range of ammunition types

The analysis of organic and inorganic gunshot residue from a single sample

The detection and interpretation of gunshot residue (GSR) can play an important role in the investigation of firearm related incidents. Recently, the potential of organic compounds to provide an additional means to discriminate between GSR and environmental particles, in particular in cases where lead-free ammunition is used, has been highlighted. This work describes a method for the extraction and detection of complementary organic and inorganic compounds from a single GSR sample, using a methodology that makes implementation in the current standard procedure feasible. GSR samples were collected from the shooter’s hands following double and single discharges, using the traditional adhesive carbon aluminium stubs. Analysis of organic compounds was performed using solid-phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), followed by analysis of the traditional inorganic particles using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). Detection of both categorised organic GSR compounds (e.g. ethyl centralite, diphenylamine and 2-nitrodiphenylamine) and characteristic inorganic GSR has been achieved. Given the fact that the detected organic GSR compounds are relevant with respect to the confirmation of GSR materials, this method has successfully demonstrated the ability to obtain a total chemical profile from a single GSR sample, which has the potential to increase the probative value of GSR evidence

Applications of Direct Injection Soft Chemical Ionisation-Mass Spectrometry for the Detection of Pre-blast Smokeless Powder Organic Additives

Analysis of smokeless powders is of interest from forensics and security perspectives. This article reports the detection of smokeless powder organic additives (in their pre-detonation condition), namely the stabiliser diphenylamine and its derivatives 2-nitrodiphenylamine and 4-nitrodiphenylamine, and the additives (used both as stabilisers and plasticisers) methyl centralite and ethyl centralite, by means of swab sampling followed by thermal desorption and direct injection soft chemical ionisation-mass spectrometry. Investigations on the product ions resulting from the reactions of the reagent ions H3O+ and O2+ with additives as a function of reduced electric field are reported. The method was comprehensively evaluated in terms of linearity, sensitivity and precision. For H3O+, the limits of detection (LoD) are in the range of 41-88 pg of additive, for which the accuracy varied between 1.5 and 3.2%, precision varied between 3.7 and 7.3% and linearity showed R20.9991. For O2+, LoD are in the range of 72 to 1.4 ng, with an accuracy of between 2.8 and 4.9% and a precision between 4.5 and 8.6% and R20.9914. The validated methodology was applied to the analysis of commercial pre-blast gun powders from different manufacturers.(VLID)4826148Accepted versio

A direct proofreader-clamp interaction stabilizes the Pol III replicase in the polymerization mode

<p>Processive DNA synthesis by the alpha epsilon theta core of the Escherichia coli Pol III replicase requires it to be bound to the beta(2) clamp via a site in the a polymerase subunit. How the epsilon proofreading exonuclease subunit influences DNA synthesis by alpha was not previously understood. In this work, bulk assays of DNA replication were used to uncover a non-proofreading activity of epsilon. Combination of mutagenesis with biophysical studies and single-molecule leading-strand replication assays traced this activity to a novel beta-binding site in e that, in conjunction with the site in a, maintains a closed state of the alpha epsilon theta-beta(2) replicase in the polymerization mode of DNA synthesis. The epsilon-beta interaction, selected during evolution to be weak and thus suited for transient disruption to enable access of alternate polymerases and other clamp binding proteins, therefore makes an important contribution to the network of protein-protein interactions that finely tune stability of the replicase on the DNA template in its various conformational states.</p>