Gunshot Residue Analysis Research Articles

Attenuated Total Reflectance-FT-IR Spectroscopy for Gunshot Residue Analysis: Potential for Ammunition Determination

The ability to link a suspect to a particular shooting incident is a principal task for many forensic investigators. Here, we attempt to achieve this goal by analysis of gunshot residue (GSR) through the use of attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FT-IR) combined with statistical analysis. The firearm discharge process is analogous to a complex chemical process. Therefore, the products of this process (GSR) will vary based upon numerous factors, including the specific combination of the firearm and ammunition which was discharged. Differentiation of FT-IR data, collected from GSR particles originating from three different firearm-ammunition combinations (0.38 in., 0.40 in., and 9 mm calibers), was achieved using projection to latent structures discriminant analysis (PLS-DA). The technique was cross (leave-one-out), both internally and externally, validated. External validation was achieved via assignment (caliber identification) of unknown FT-IR spectra from unknown GSR particles. The results demonstrate great potential for ATR-FT-IR spectroscopic analysis of GSR for forensic purposes.

Integrated Ion Beam Analysis (IBA) in Gunshot Residue (GSR) characterisation

Gunshot Residue (GSR) is residual material from the discharge of a firearm, which frequently provides crucial information in criminal investigations. Changes in ammunition manufacturing are gradually phasing out the heavy metals on which current forensic GSR analysis is based, and the latest Heavy Metal Free (HMF) primers urgently demand new forensic solutions. Proton scanning microbeam Ion Beam Analysis (IBA), in conjunction with the Scanning Electron Microscope equipped with an Energy Dispersive X-ray Spectrometer (SEM-EDS), can be introduced into forensic analysis to solve both new and old problems, with a procedure entirely commensurate with current forensic practice. Six cartridges producing GSR particles known to be interesting in casework by both experience and the literature were selected for this study. A standard procedure to relocate the same particles previously analysed by SEM-EDS, based on both secondary electron (SE) and X-ray imaging was developed and tested. Elemental Particle Induced X-ray Emission (PIXE) mapping of the emitted X-rays allowed relocation in a scan of 10μm×10μm of even a 1μm GSR particle. The comparison between spectra from the same particle obtained by SEM-EDS and IBA-PIXE showed that the latter is much more sensitive at mid-high energies. Results that are very interesting in a forensic context were obtained with particles from a cartridge containing mercury fulminate in the primer. Particle-induced gamma-ray emission (PIGE) maps of a particles from HMF cartridges allowed identification of Boron and Sodium in particles from hands using the 10B(p,α1γ)7Be, 11B(p,p1γ)11B and 23Na(p,p1γ)23Na reactions, which is extraordinary in a forensic context. The capability for quantitative analysis of elements within individual particles by IBA was also demonstrated, giving the opportunity to begin a new chapter in the research on GSR particles. The integrated procedure that was developed, which makes use of all the IBA signals, has unprecedented characterisation and discrimination power for GSR samples

Analysis of macroscopic gunshot residues by Raman spectroscopy to assess the weapon memory effect

Gunshot residues (GSR) are valuable evidence which provide the forensic analyst with useful information about a crime scene when proper analytical methods are used. Nowadays, the method of choice for analyzing GSR is scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM/EDX). However, SEM/EDX presents limitations when the GSR identification of “non-toxic” ammunition types is performed. To overcome this drawback, Raman spectroscopy has been recently proposed as a complementary technique to SEM/EDX. However, for the time being, it can only be used in a limited number of casework (e.g. examining the macroscopic GSR produced at short distance over victim's clothes) and further research to know when this technique could support SEM–EDX results is required.In the present work, the memory effect of the weapon, which plays an important role to link the GSR found and the ammunition fired, is studied. Twenty shots were fired at close distance (∼30cm) at paper targets using the same weapon with two different types of ammunition. The first, third, ninth, and twentieth shots were fired with the first ammunition and the shots among them using the second ammunition. The macroscopic GSR produced by the first ammunition were analyzed using Raman spectroscopy. First, the spectra obtained were visually differentiated by taking into account the band at about 1342cm−1. This first approach shown that in the first shot were no GSR particles from the second ammunition, but 1.5–7.5% of analyzed particles corresponded to the second ammunition in the third, ninth, and twentieth shots. Additionally, the same differentiation was then performed by discriminant analysis using the spectral range from 1800 to 800cm−1. Although using this second approach only one GSR was identified as the second ammunition, was remarkable that after the shots with different ammunition the GSR obtained shows greater variability. The results obtained suggest that the memory effect of the weapon has not a significant influence when the organic analysis of macroscopic GSR on targets by Raman spectroscopy is performed.

Electrochemical Detection of Gunshot Residue for Forensic Analysis: A Review

AbstractCurrent demands for detection of Gunshot Residue (GSR) require a reliable and rapid decentralized detection system with high sensitivity and specificity. This article reviews the use of electrochemical devices for GSR detection over the last 35 years and highlights recent advances associated with the demands of GSR field detection such as portability, speed, cost and power. Anodic stripping voltammetry (ASV) has been widely implemented for the detection of the metallic components of GSR at a variety of working electrodes. Efforts toward the detection of the organic components of GSR have also been reported using cyclic‐ and square‐wave voltammetry. The simultaneous detection of both organic and inorganic GSR constituents has recently been examined to increase the overall information content in a single voltammetric scan. As well as this, exploitation of screen‐printing fabrication allows replacement of conventional electrochemical cells with easy‐to‐use sensor strips Sampling methods for electrochemical GSR analysis are also advancing from acid washes or swabs to simpler abrasive methods which integrate sampling and analysis obviating the need for intermediate processing steps. The latest direction of electrochemical detection of GSR involves chemometric treatment to evaluate data allowing for more objective conclusions and increasing the automation of the system. These advances indicate great promise for investigating firearm‐related crimes, and bring significant changes to the detection of GSR making electroanalysis a powerful tool for decentralized forensic analysis.

Gunshot residue analysis and its evidential values: a review

Gunshot residue analysis has revealed vital trace evidence consequent to the criminal use of firearms. In forensic investigations, gunshot residue examination is sought for solving a wide range of issues from identification of a shooter to relating a bullet with the wound in reconstructing crime involving firearm. Thus, a review of analytical techniques that had been found useful for such context-oriented analysis is considered relevant. Besides the methods in forensic gunshot residue analysis, this review highlights the evidential values of organic and inorganic gunshot residues analysis that can relate a person, the place and the time with the firearm involved.

Advanced statistical analysis and discrimination of gunshot residue implementing combined Raman and FT-IR data

We report a novel analytical and statistical approach to gunshot residue (GSR) analysis, characterization and discrimination. Spectroscopic data from two complementary techniques (Raman and FT-IR) were combined into a single dataset to improve statistical discrimination of GSR.

A new quantitative method for gunshot residue analysis by ion beam analysis

Imaging and analyzing gunshot residue (GSR) particles using the scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDS) is a standard technique that can provide important forensic evidence, but the discrimination power of this technique is limited due to low sensitivity to trace elements and difficulties in obtaining quantitative results from small particles. A new, faster method using a scanning proton microbeam and Particle Induced X-ray Emission (μ-PIXE), together with Elastic Backscattering Spectrometry (EBS) is presented for the non-destructive, quantitative analysis of the elemental composition of single GSR particles. In this study, the GSR particles were all Pb, Ba, Sb. The precision of the method is assessed. The grouping behaviour of different makes of ammunition is determined using multivariate analysis. The protocol correctly groups the cartridges studied here, with a confidence >99%, irrespective of the firearm or population of particles selected.

Preliminary evaluation of the persistence of organic gunshot residue

The organic components of gunshot residue (OGSR, also called firearms discharge residue (FDR) or cartridge discharge residue (CDR)) have been studied and discussed in the literature. These residues, consisting of particulates such as burned and unburned powder as well as molecular compounds, are rarely used in casework except for purposes such as shooting reconstructions. Molecular compounds that survive the firing event or that are created as a result of the firing event could, with focused research and development, open a new avenue for forensic gunshot residue analysis. In this study, the persistence of organic gunshot residue was evaluated using diphenylamine (DPA) as a target analyte and ion mobility spectrometry (IMS) as the detection system. Samples were collected from hands using a solvent swabbing technique and the swab was analyzed using direct thermal desorption for sample introduction into the IMS. OGSR was found to persist for at least 4h. Although DPA is a widely used industrial compound, analysis of numerous blank and background samples (n∼100) did not show any significant response for DPA using this detector. Variations were noted among individuals and as such, the data set does not support estimation of a half-life as has been done for traditional primer residues. No secondary transfers were observed, suggesting the possibility of skin adhesion via interactions between the lipophilic organic compounds and skin lipids. IMS proved valuable as a means of generating patterns for forensic pattern matching and shows promise as a screening tool applied to firearms discharge.

Munition related metals - Combined toxicity of Antimony, Copper, and Lead

The identification of characteristic organic gunshot residues (OGSR) provides conclusive evidence in the elucidation of elemental profiles when lead-free ammunition is fired. OGSR also prevents false negatives. Toward this aim, a quick and efficient method based on liquid chromatography–quadrupole time-of-flight mass spectrometry (LC–QTOF) was developed to detect and identify 18 gunpowder additives in gunshot residues (GSR). The unequivocal identification of target analytes was assured by using MS/MS mode. Swabs were compared with home-modified tape lift supports covered with a PTFE layer to determine the better sampling technique. The modified tape lift provided better extraction recoveries and enabled the analysis of inorganic and organic GSR simultaneously. The developed method was applied to the analysis of GSR from four different lead-free ammunitions. Diphenylamine and its nitrated degradation products and centralites were identified in all samples, providing strong evidence of GSR.

Characterisation of gunshot residue from three ammunition types using suppressed anion exchange chromatography

Gunshot residue (GSR) is commonly analysed in forensic casework using either scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) or gas chromatography-mass spectrometry (GC-MS). Relatively little work has been reported on the post-discharge GSR content of non-metallic inorganic or low molecular weight organic anions to distinguish between different ammunition types. The development of an analytical method using suppressed micro-bore anion exchange chromatography (IC) is presented for the analysis of GSR. A hydroxide gradient was optimised for the separation of 19 forensically relevant organic and inorganic anions in <23min and sensitivities of the order of 0.12-3.52ng of anion detected for all species were achieved. Along with an optimised extraction procedure, this method was applied to the analysis of post-ignition residues from three selected ammunition types. By profiling and comparing the anionic content in each ammunition residue, the possibility to distinguish between each type using their anionic profiles and absolute weight is presented. The potential for interference is also discussed with respect to sample types which are typically problematic in the analysis of GSR using SEM-EDX and GC-MS. To the best of our knowledge this represents the first study on the analysis of inorganic anions in GSR using suppressed ion chromatography.

Ammunition Identification by Means of the Organic Analysis of Gunshot Residues Using Raman Spectroscopy

The ability to unequivocally identify a gunshot residue (GSR) when a firearm is discharged is a very important and crucial part of crime scene investigation. To date, the great majority of the analyses have focused on the inorganic components of GSR, but the introduction of "lead-free" or "nontoxic" ammunitions makes it difficult to prevent false negatives. This study introduces a fast methodology for the organic analysis of GSR using Raman spectroscopy. Six different types of ammunition were fired at short distances into cloth targets, and the Raman spectra produced by the GSR were measured and compared with the spectra from the unfired gunpowder ammunition. The GSR spectrum shows high similarity to the spectrum of the unfired ammunition, allowing the GSR to be traced to the ammunition used. Additionally, other substances that might be found on the victim's, shooter's, or suspect's clothes and might be confused with GSR, such as sand, dried blood, or black ink from a common ballpoint pen, were analyzed to test the screening capability of the Raman technique. The results obtained evidenced that Raman spectroscopy is a useful screening tool when fast analysis is desired and that little sample preparation is required for the analysis of GSR evidence.

Distribution of gunshot residues – The influence of weapon type

Gunshot residue (GSR) analysis is a frequently used forensic method for investigating shooting events. In this process, GSR-particles are detected on pertinent objects, often the hands of a suspect, with energy dispersive X-ray microanalysis in a scanning electron microscope. The question asked in court is usually the following: "… has or has not a given shot been fired by the suspect (at a certain place and time)?" Unfortunately, this question frequently cannot be answered by the analyst. Only the presence or absence of "characteristic" GSR-particles on the investigated sample can be stated with confidence. All other assumptions are inherently biased by many factors that are usually only known by the culprit or are generally unknown. In order to draw more profound conclusions from GSR analytical results, the dynamics of GSR particles have to be considered, i.e., how these particles reach a suspect. Consequently, the formation of the plume after firing was investigated for eleven different firearms with high speed-video analysis. The results show that a vast scope exists between revolvers - distributing many particles near the shooter - and e.g. shotguns that are quite sealed. These differences between the various weapon types should be considered for interpretation of the results of GSR-analysis.

Estimating the time since discharge of spent cartridges: A logical approach for interpreting the evidence

Estimating the time since discharge of a spent cartridge or a firearm can be useful in criminal situations involving firearms. The analysis of volatile gunshot residue remaining after shooting using solid-phase microextraction (SPME) followed by gas chromatography (GC) was proposed to meet this objective. However, current interpretative models suffer from several conceptual drawbacks which render them inadequate to assess the evidential value of a given measurement. This paper aims to fill this gap by proposing a logical approach based on the assessment of likelihood ratios. A probabilistic model was thus developed and applied to a hypothetical scenario where alternative hypotheses about the discharge time of a spent cartridge found on a crime scene were forwarded. In order to estimate the parameters required to implement this solution, a non-linear regression model was proposed and applied to real published data. The proposed approach proved to be a valuable method for interpreting aging-related data.

The survival of metallic residues from gunshot wounds in cremated bone: a SEM–EDX study

The research and analysis of gunshot residues has a relevant role in the examination of gunshot wounds. Nevertheless, very little literature exists concerning gunshot wounds on charred material. In this study, 16 adult bovine ribs (eight still with soft tissues and eight totally skeletonized) underwent a shooting test with two types of projectiles (9mm full metal-jacketed bullet and 9mm unjacketed bullet). Each rib then underwent a charring process in an electric oven, reaching the stage of complete calcination at 800°C. The area of each entrance wound was analyzed before and after the carbonization process via a scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDX). In each sample, metallic residues composed of lead, barium, and antimony were found. These metallic residues were thus preserved also after exposure to the extremely high temperatures reached within the oven, especially with unjacketed bullets, although the particles seem to be more irregular in shape as a result of the heating process. In conclusion, this study proved that gunshot residues survive extremely high temperatures and can be detected via SEM/EDX even in cases of charred tissues.

Differentiation of Bullet Type Based on the Analysis of Gunshot Residue Using Inductively Coupled Plasma Mass Spectrometry*

Porcine tissue samples shot with two different types of bullets, jacketed and nonjacketed, were collected in the fresh state and throughout moderate decomposition. Wound samples were microwave-digested and analyzed using inductively coupled plasma mass spectrometry (ICP-MS) to detect all elements present at measurable levels in gunshot residue (GSR). Elements detected included antimony (Sb), barium (Ba), and lead (Pb), which are considered characteristic of GSR, as well as iron (Fe) and copper (Cu). These five elements were used to differentiate shot tissue and unshot tissue, as well as tissue shot by the two different bullet types, both in the fresh state and throughout moderate decomposition. The concentrations of Cu, Sb, and Pb were able to distinguish the two bullet types in fresh tissue samples at the 95% confidence level. Cu and Pb were able to differentiate the bullet types throughout moderate decomposition at the 99% confidence level.

Chemical analysis of firearms, ammunition, and gunshot residue — James Smyth Wallace

Chemical analysis of firearms, ammunition, and gunshot residue — James Smyth Wallace

Primer composition and memory effect of weapons—Some trends from a systematic approach in casework

Since 2008, our laboratory has adopted a systematic approach to the examination of gunshot residues (GSR) in casework by analysing, whenever possible, the inorganic composition present in ammunition (cartridge cases and unused ammunition). By compiling the results of these analyses in a database, it is possible to observe some trends during the period of interest: on the one hand, the prevalence of primers containing lead, barium and antimony is about 50%, and even as high as 70% when including lead-barium-antimony based primers also containing tin; on the other hand, the prevalence of non-toxic primers is for the time being very low. Still using the same approach, test firings were performed with recovered weapons and litigious ammunition whenever possible in order to estimate the influence of the well known "memory effect" of the weapons on the GSR analysis results. The first results show a quite strong memory effect for the .22 and the .32 caliber, unlike the .38 caliber. This is probably due to a high prevalence of lead-barium-antimony based primers for the latter caliber.

High Photoluminescent Metal–Organic Frameworks as Optical Markers for the Identification of Gunshot Residues

Gunshot residue (GSR) are solid particles produced when a firearm is discharged, and its detection is important evidence in forensic investigations. Currently, scanning electron microscopy coupled to energy dispersive spectroscopy (SEM-EDS) is the standard technique adopted for the analysis and identification of GSR; however, this methodology is inefficient for lead-free ammunition. Herein, we report the inclusion of high photoluminescent metal-organic frameworks in ammunition to allow for the visual detection of GSR. The tests indicated that marked GSR is easily visible in proportions above 5.0 wt %. A total of 1 g of marker suffices to tag 100 0.38 mm bullets or 62 0.40 mm bullets.

Application of X-ray Photoelectron Spectroscopy (XPS) for the Surface Characterization of Gunshot Residue (GSR)

Gunshot residue (GSR) is typically found on the hands or clothing of persons who have been in the environment of a discharging firearm, but it may also be found on objects in the vicinity of the discharge. Computer-controlled scanning electron microscopy (CCSEM) is the method preferred by the forensic community for the automated analysis of GSR. GSR samples are therefore typically collected from a crime suspect's hands and/or clothing using SEM sample stubs coated with a conductive adhesive. The three major components in modern firearm cartridge primers are lead styphanate (initiator), antimony sulfide (fuel), and barium nitrate (oxidizer). GSR consists of the products of combustion of these primer materials. Large populations of particles in the size range of ~1–10 μm are rapidly screened by energy-dispersive X-ray spectroscopy (EDS) for the presence of combinations of Pb, Sb, and Ba. When combinations of these three elements are detected, the particles are flagged as potential GSR particulate. Flagged particles with significant Pb/Sb/Ba compositions are subsequently relocated for a live identification and a positive confirmation of GSR. Positive particles are classified as being either “characteristic of GSR” (that is, all three key elements are present) or “consistent with GSR” (that is, any two of the key elements are present) based on the particle composition and morphology. Classification is based on the presence of the constituent elements and is not dependant on the element amounts. If a particle does not meet the proper compositional or morphological criteria, it is rejected as GSR. However, CCSEM generally does not provide information regarding the population of particles much less than 1 μm or the surface chemistry of the GSR particles. This article examines the fine fraction of GSR particles with high-resolution electron microscopy and complements the microscopy data with surface chemistry information from X-ray photoelectron spectroscopy (XPS).

Gunshot Residue Analysis in the Undergraduate Laboratory Using Toy Cap Guns

ABSTRACT The authors developed an experiment for the undergraduate analytical or forensic chemistry laboratory in which gunshot residues (GSRs) produced from toy cap guns are analyzed by laser-induced breakdown spectroscopy (LIBS). Alternatively, the experiment is readily adaptable to any emission spectroscopy technique. This project allows students to investigate the development of a forensic method while addressing proper sampling techniques used in forensic investigations. Students were able to develop a library of blank samples, establish signal detection limits to address legal considerations for determination of false-positive and -negative error rates, and optimize an emission spectrometer.