Detection of gunshot residues using mass spectrometry

In recent years, forensic scientists have become increasingly interested in the detection and interpretation of organic gunshot residues (OGSR) due to the increasing use of lead- and heavy metal-free ammunition. This has also been prompted by the identification of gunshot residue- (GSR-) like particles in environmental and occupational samples. Various techniques have been investigated for their ability to detect OGSR. Mass spectrometry (MS) coupled to a chromatographic system is a powerful tool due to its high selectivity and sensitivity. Further, modern MS instruments can detect and identify a number of explosives and additives which may require different ionization techniques. Finally, MS has been applied to the analysis of both OGSR and inorganic gunshot residue (IGSR), although the "gold standard" for analysis is scanning electron microscopy with energy dispersive X-ray microscopy (SEM-EDX). This review presents an overview of the technical attributes of currently available MS and ionization techniques and their reported applications to GSR analysis. © 2014 Regina Verena Taudte et al

A portable explosive detector based on fluorescence quenching of pyrene deposited on coloured wax-printed μpADs

A new technique for the detection of explosives has been developed based on fluorescence quenching of pyrene on paper-based analytical devices (μPADs). Wax barriers were generated (150 °C, 5 min) using ten different colours. Magenta was found as the most suitable wax colour for the generation of the hydrophobic barriers with a nominal width of 120 μm resulting in fully functioning hydrophobic barriers. One microliter of 0.5 mg mL-1 pyrene dissolved in an 80 : 20 methanol-water solution was deposited on the hydrophobic circle (5 mm diameter) to produce the active microchip device. Under ultra-violet (UV) illumination, ten different organic explosives were detected using the μPAD, with limits of detection ranging from 100-600 ppm. A prototype of a portable battery operated instrument using a 3 W power UV light-emitting-diode (LED) (365 nm) and a photodiode sensor was also built and evaluated for the successful automatic detection of explosives and potential application for field-based screening. © 2013 The Royal Society of Chemistry

Matching sensitivity to abundance: High resolution immuno-mass spectrometry imaging of lanthanide labels and endogenous elements in the murine brain

© 2020 The Royal Society of Chemistry. This work introduces a new method for immuno-mass spectrometry imaging via quadrupole-based laser ablation-inductively coupled plasma-mass spectrometry instruments that is matched to the abundance of elements in biological tissues. Manipulation of ion-optics and quadrupole mass filter parameters provided increased transmission of low level high-mass elements, which are typically used as labels for antibodies, at the expense of highly abundant endogenous low-mass elements. Transmission of mid-mass elements such as transition metals was only slightly affected. The implications for mass resolution and background signals are critically discussed and signal to noise ratios and imaging capabilities are compared to those obtained from a standard method. This novel approach resulted in a 6-fold improved signal to noise ratio for lanthanides that are routinely used as elemental labels for antibodies to target protein distributions in biological tissues. This increase in signal intensity, enhanced contrasts, lower limits of detection and the potential to improve spatial resolution contributed to enhanced imaging and trace analyses, as demonstrated by imaging murine brain sections of the hippocampal system and substantia nigra

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

Stability of smokeless powder compounds on collection devices

© 2016 Elsevier Ireland Ltd The current trend towards the implementation of organic gunshot residue (OGSR) analysis into gunshot residue (GSR) investigation protocols typically involves the sequential analysis of inorganic and organic GSR. However, to allow for the consecutive analysis of inorganic and organic GSR, specimens will often be stored for different lengths of time which may result in compounds of interest degrading. In order to optimise storage conditions, it is important to consider compound degradation on collection devices during storage. This study investigated the degradation over time of compounds potentially present in smokeless powders and OGSR on two collection devices, alcohol swabs and GSR stubs. Over a period of 63 days, the highest degree of degradation was found in the first four days. Interestingly, energetic compounds were generally found to be more stable than smokeless powder additives such as stabilisers including diphenylamine and ethyl centralite, which might be problematic considering that these compounds are common targets for OGSR. The findings can provide valuable information to operational forensic laboratories to optimise their storage durations

Using paper-based microfluidics and lab on a chip techonologies for the rapid analysis of trinitro aromatic explosives

© 14CBMS. We report a new microfluidic paper-based analytical device (μPAD) containing potassium hydroxide to create a color change reaction when in contact with trinitro aromatic explosives, followed by extraction and lab on a chip analysis. The procedure allowed the detection and identification of 1 μg of the target explosives distributed on a 100 cm2surface

High-throughput screening for target compounds in smokeless powders using online-SPE tandem mass spectrometry

© 2019, © 2019 Australian Academy of Forensic Sciences. The detection and quantification of compounds present in smokeless powders plays an important role in various fields such as environmental and forensic science. Often, time and labour consuming sample preparation techniques such as solid phase extraction (SPE) are required to facilitate either pre-concentration or sample clean-up with complex matrices. This paper describes the first application of the completely automated online SPE system RapidFire® connected to a triple quadrupole mass spectrometer for smokeless powder/gunshot residue analysis. The optimized method involved sample loading during 2000 ms using UP water (0.1% formic acid) at a flowrate of 1.25 mL/min on a Type C C18 cartridge followed by elution of the target compounds for 3000 ms using IPA (0.1% formic acid) at 0.75 mL/min. Target compounds were detected in soil (DPA, 2-NDPA, EC, NG, 2,4-DNT) and cotton swabs (NG) in only 8 seconds per sample with detection limits of 0.223 ppm (DPA), 0.104 ppm (2-NDPA), 0.0949 ppm (EC), 0.187 ppm (NG) and 0.128 ppm (2,4-DNT). The presented method showed promising results for the analysis of five target analytes in soil samples. Further optimisations can extend the analysis to other sample matrices and include more analytes potentially present in smokeless powders and GSR

Headspace analysis of E-cigarette fluids using comprehensive two dimensional GC×GC-TOF-MS reveals the presence of volatile and toxic compounds.

The analysis of electronic cigarrete (E-cigarette) fluids by high performance liquid chromatography or gas chromatography (GC) coupled to mass spectrometry (MS), GC hyphenated to flame-ionisation detection, or nuclear magnetic resonance spectroscopy poses many challenges due to the complex matrix and extremely high number of compounds present. In order to overcome these challenges, this study focused on the detection of the multiple complex compounds classes produced by the pyrolysis of E-cigarette liquids using comprehensive two dimensional gas chromatography (GCxGC) coupled to time of flight (TOF)-MS. Gas samples were prepared by heating E-liquids inside aluminium tins for 5 min. The tins were placed in a sand bath, which was temperature controlled at 200 °C. The samples were collected using thermal desorption tubes connected to volatile organic compound (VOC) sampling pump attached and subsequently analysed using GCxGC-TOF-MS. The greater peak resolution obtained when using GCxGC-TOF-MS allowed to distinguish many toxic compounds and VOCs that could not be detected by the other methods mentioned above. As a result, a comprehensive list of volatile compounds emitted from E-cigarette fluids when heated was established, which might allow a better understanding of potential health effects of vaping. Heating E-liquids to moderate temperature results in the emission of over 1000 volatile compounds of which over 150 are toxic. These compounds are either present in the liquid or can be formed during storage or heating leading to a more complex volatile profile of E-cigarette liquids than previously assumed. The application of GCxGC-TOF-MS allows the elucidation of this profile and therefore a better understanding of possible health implications

Development of a UHPLC method for the detection of organic gunshot residues using artificial neural networks

© The Royal Society of Chemistry. The introduction of lead and heavy-metal free ammunition to the market challenges the current protocol for gunshot residue (GSR) investigations, which focuses on the inorganic components. Future proofing GSR analysis requires the development and implementation of new methods for the collection and analysis of organic GSR (OGSR) into operational protocols. This paper describes the development and optimisation of an ultra high performance liquid chromatography method for the analysis of 32 compounds potentially present in OGSR. An artificial neural network was applied to predict the retention times of the target analytes for various gradients for rapid determination of optimum separation conditions. The final separation and analysis time for the 32 target analytes was 27 minutes with limits of detection ranging from 0.03 to 0.21 ng. The method was applied to the analysis of smokeless powder and samples collected from the hands of a shooter following the discharge of a firearm. The results demonstrate that the method has the potential for use in cases involving GSR

Coupling paper-based microfluidics and lab on a chip technologies for confirmatory analysis of trinitro aromatic explosives

A new microfluidic paper-based analytical device (μPAD) in conjunction with confirmation by a lab on chip analysis was developed for detection of three trinitro aromatic explosives. Potassium hydroxide was deposited on the μPADs (0.5 μL, 1.5 M), creating a color change reaction when explosives are present, with detection limits of approximately 7.5 ± 1.0 ng for TNB, 12.5 ± 2.0 ng for TNT and 15.0 ± 2.0 ng for tetryl. For confirmatory analysis, positive μPADs were sampled using a 5 mm hole-punch, followed by extraction of explosives from the punched chad in 30 s using 20 μL borate/SDS buffer. The extractions had efficiencies of 96.5 ± 1.7%. The extracted explosives were then analyzed with the Agilent 2100 Bioanalyzer lab on a chip device with minimum detectable amounts of 3.8 ± 0.1 ng for TNB, 7.0 ± 0.9 ng for TNT, and 4.7 ± 0.2 ng for tetryl. A simulated in-field scenario demonstrated the feasibility of coupling the μPAD technique with the lab on a chip device to detect and identify 1 μg of explosives distributed on a surface of 100 cm2. © 2014 American Chemical Society