A simple method for detection of gunshot residue particles from hands, hair, face, and clothing using scanning electron microscopy/wavelength dispersive X-ray (SEM/WDX).

We devised a simple and rapid method for detection of gunshot residue (GSR) particles, using scanning electron microscopy/wavelength dispersive X-ray (SEM/WDX) analysis. Experiments were done on samples containing GSR particles obtained from hands, hair, face, and clothing, using double-sided adhesive coated aluminum stubs (tape-lift method). SEM/WDX analyses for GSR were carried out in three steps: the first step was map analysis for barium (Ba) to search for GSR particles from lead styphnate primed ammunition, or tin (Sn) to search for GSR particles from mercury fulminate primed ammunition. The second step was determination of the location of GSR particles by X-ray imaging of Ba or Sn at a magnification of x 1000-2000 in the SEM, using data of map analysis, and the third step was identification of GSR particles, using WDX spectrometers. Analysis of samples from each primer of a stub took about 3 h. Practical applications were shown for utility of this method.     

Glass-containing gunshot residue particles: a new type of highly characteristic particle?

In 0.22 caliber rimfire ammunition, the primer often contains lead or lead and barium compounds. As residues from these primers do not contain lead, barium, and antimony, they cannot be uniquely classified as gunshot residue (GSR) under ASTM designation E 1588-95. In many types of 0.22 caliber rimfire ammunition, the cartridge contains a primer sensitized with glass. In this paper we describe a previously unreported type of GSR particle consisting of glass fused with other primer components. As there appear to be few potential environmental or occupational sources of particles composed of lead and barium compounds fused to glass, particularly borosilicate glass, these particles may have high evidential value. Scanning electron microscopy with energy dispersive X-ray detection (SEM-EDX) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were evaluated for the characterization of glass-containing GSR particles. The occurrence of glass-containing GSR particles was established in the residue from various brands of 0.22 caliber ammunition, and several sub-types were identified.     

Crime scene investigations using portable,non-destructive space exploration technology

The National Institute of Justice (NIJ) and the National Aeronautics and Space Administration's (NASAs) Goddard Space Flight Center (GSFC) have teamed up to explore the use of NASA developed technologies to help criminal justice agencies and professionals solve crimes. The objective of the program is to produce instruments and communication networks that have application within both NASA's space program and NIJ programs with state and local forensic laboratories. A working group of NASA scientists and law enforcement professionals has been established to develop and implement a feasibility demonstration program. Specifically, the group has focused its efforts on identifying gunpowder and primer residue, blood, and semen at crime scenes. Non-destructive elemental composition identification methods are carried out using portable X-ray fluorescence (XRF) systems. These systems are similar to those being developed for planetary exploration programs. A breadboard model of a portable XRF system has been constructed for these tests using room temperature silicon and cadmium-zinc telluride (CZT) detectors. Preliminary tests have been completed with gunshot residue (GSR), blood-spatter and semen samples. Many of the element composition lines have been identified. Studies to determine the minimum detectable limits needed for the analyses of GSR, blood and semen in the crime scene environment have been initiated and preliminary results obtained. Furthermore, a database made up of the inorganic composition of GSR is being developed. Using data obtained from the open literature of the elemental composition of barium (Ba) and antimony (Sb) in handswipes of GSR, we believe that there may be a unique GSR signature based on the Sb to Ba ratio.     

A comparative study of gunshot residue originating from 9 mm Luger ammunition from various producers

Following previous work on differentiation between gunshot residue according to the type of ammunition used, a specific investigation was undertaken of traces originating from 9 mm Luger ammunition using SEM-EDX. The aim of this study was to determine whether GSR originating from this type of ammunition is similar, or whether differentiation could be made between particular manufacturers of Luger ammunition. The results were collected in the form of counts of particles in each of seven key elemental classes being combinations of lead, antimony and barium. These were then adjusted to a factor known as frequency of occurrence which allows comparison of the distribution of particles within the classes between samples with differences in absolute particle counts. The relationships between the samples were examined using non-parametric statistical tests: R-Spearman and tau-Kendall rank correlation coefficients. It has been found that most of the studied samples of GSR were similar to each other despite their originating from various manufacturers.     

Brake linings: a source of non-GSR particles containing lead,barium, and antimony

The observation of environmental particles similar in composition to gunshot residue (GSR) are not new to forensic experts and have been described in the scientific literature. In order to better define the origin of these particles, brake linings and their wear products were examined by SEM-EDX. The results obtained demonstrate that some types of brake linings contain lead, barium, and antimony and that they can represent a source of particles showing GSR-like elemental profiles. Most of these particles can be easily discriminated from primer discharge residue because of the high levels of iron or the presence of "prohibited" elements in the spectrum. However, particles with iron at minor or trace levels and lacking "prohibited" elements were also found. It is thus advisable to use caution when describing the composition of similar particles as "unique" to primer discharge residue. The strict application of a rigorous morphological criterion is also recommended.     

Handguns and ammunitions indicators extracted from the GSR analysis

The computer automated scanning electron microscope. X-ray microanalysis of Firearms Discharge Residue (FDR) can reveal substantial information about the circumstances of their generation beyond the presence of characteristic gunshot residue (GSR). Indicators of the type of weapon and ammunition used can he obtained from the distribution of GSR particle shapes and from the multi-element analysis of the FDR sample. This is demonstrated for a large database of GSR samples from nine different handguns and over 60 different ammunitions. An example classification scheme is presented for the supporting particles generally found present in FDR. When particle type area concentration ratios are normalized to the iron (Fe) particle type, results show it is possible to distinguish much about the metal used in the weapon manufacture, whether it was of large or small caliber, whether the bullets were jacketed or plated, and whether the cartridge cases were of aluminum, brass, or nickel-plated brass. Standardization of such analytical schemes would be advantageous.     

A versatile technique for the investigation of gunshot residue patterns on fabrics and other surfaces: m-XRF

With heavy-metal-free ammunitions becoming more and more popular, it is necessary to find methods to visualize patterns of those elements in gunshot residues (GSRs) that are not accessible by chemographic coloring tests. The recently introduced millimeter-X-ray fluorescence analysis (m-XRF) spectrometer Spectro Midex M offers an easy way to record mappings of GSRs containing such elements in order to determine shooting distances as well as the general composition of these particles. A motorized stage enables samples of a maximum size of 20 x 20 cm to be investigated, like fabric, clothes, adhesive tapes (Filmolux films), and polyvinylalcohol gloves of shooter's hands. Human tissues can be measured using a Peltier-cooled specimen holder that is mounted onto the stage. As the spot size of the exiting X-rays lies in the millimeter range, which is adequate for the assessment of the residue patterns for shooting distance determination, a significant reduction in measurement time is achieved compared with mu-XRF methods. Test shots with heavy-metal-free ammunitions were performed on different target materials, like pork skin and fabric, and the elemental distributions of Ti, K, and Ga were determined. In order to show the capability of the spectrometer for conventional lead ammunitions as well, a shot series of 5-100 cm shooting distance and an adhesive tape of a shooter's hand were investigated analogously. A comparison of several methods applied in GSR investigation shows the advantages of the m-XRF method.     

Analysis of Gunshot Residue and Associated Materials—A Review

Abstract: A comprehensive review of the scientific literature on gunshot residue (GSR) is presented. Aspects of both inorganic and organic GSR are discussed, from formation and distribution, to sample collection, preparation, and analysis using a variety of techniques. The interpretation of GSR results is also considered including issues surrounding the contamination, distribution, and transfer of GSR. Potential problems with ulterior sources of GSR like particles have been reported in the literature. For example, particles from environmental and occupational sources have been highlighted as exhibiting similar chemical and morphological characteristics to GSR. These findings are put into context with regard to interpreting samples. A move toward a “case by case” approach is argued to be more preferable to a “formal” classification system where possible. The analysis of both inorganic and organic compositions of residue samples as well as morphological considerations is considered to be a more ideal approach to GSR analysis, whereever practicable.     

Rapid search and quantitative analysis of gunshot residue particles in the SEM

Automated scanning electron microscopy coupled with image analysis and X-ray micro analysis was used to characterize a variety of gunshot residue (GSR) samples. More than 500 rounds of commercially available ammunition and six different types of hand gulls were used in the study of 17 GSR and 19 reference specimens. The individual particle X-ray composition was determined for 12 different elements. Elemental composition of GSR particles was highly variable but consistent with compounds mixed into or associated with a barium oxide matrix. When present in a specimen, GSR could be adequately characterized with automated procedures in less than an hour by restricting analyses to features larger than 2 microm. In "clean" samples, a higher resolution particle search was required to avoid reporting false negatives. Careful control of the back scattered electron signal strength threshold, by reference to a standard, was needed to ensure both time-efficient and accurate analyses. Samples collected from non-shooting subjects. active in a physical environment which contained firearms discharge residue were seen to be easily contaminated by sub-micron GSR particles.     

Analysis of primer residue from lead free ammunition by X-ray microfluorescence

In forensic science, the analysis of gunshot residues was traditionally done by the detection of lead (Pb), antimony (Sb) and barium (Ba) usually found in a primer. However, the recent development of lead-free ammunition represents a new challenge for ballistic specialists. This analysis study gunshot residues from primers and ammunitions in the area surrounding bullet holes, a very important tool to determine the shooting distance. The ammunitions used were 9 mm Luger and .38 spl + p calibers, where lead in the primer was replaced with strontium (Sr) and where the lead bullet was plated with copper (Total Metal Jacket). Gunshot analysis results were obtained using an energy dispersive X-ray microfluorescence spectrometer. The method allows the detection and quantification of strontium residues on the target up to a distance of 45 cm.     

毛发枪弹损伤的环境扫描电镜研究

目的探讨毛发枪弹损伤微观形态与射击距离之间的关系。方法应用环境扫描电镜/能谱仪对64式手枪在0~200cm范围内射击造成的毛发损伤及附着物进行形态和成分分析。结果0~30cm射击,毛发表面粘附有大量密集分布的球形射击残留物颗粒,鳞片有严重斑纹状损伤和崩裂缺损;30~60cm射击,毛发表面粘附有较多散在分布的球形射击残留物颗粒,鳞片有轻微斑纹状损伤和崩裂缺损;100cm距离射击,毛发表面粘附有少数个别射击残留物颗粒,鳞片无斑纹状损伤;200cm距离射击,毛发表面无射击残留物。毛发枪弹射击断裂形态差异较大,大体分为剪切断裂和牵拉断裂两种类型,与射击距离无明显相关性。结论毛发表面粘附的大量球形射击残留物颗粒及其造成的鳞片斑纹状损伤对于法医学鉴定贴近距离射击((30cm)具有重要的实用价值。     

Automated SEM/EDS Analysis of Airbag Residue. II: Airbag Residue as a Source of Percussion Primer Residue Particles

Abstract:  Automated scanning electron microscopy with energy dispersive spectroscopy has been used to analyze airbag residue particles. Analysis of airbag residue from some passenger side airbags revealed some residue particles which are consistent with gunshot residue (GSR) samples. The source of these particles was determined to be percussion primers used to initiate the chemical reaction for deployment. This article identifies some vehicles which contain this type of airbag and demonstrates the types of particles which could be misidentified as being GSR. The low numbers of GSR particles in among the large particle populations of zirconium and/or copper–cobalt particles, which are clearly airbag residue, allow the trained analysts to distinguish the correct source of this residue. Particles containing high aluminum levels, elevated levels of allowable elements in GSR particles, or the presence of elements that are rare in GSR particles stand out as indications that the particles are not GSR in origin. This study serves as a guide to analysts who perform particle analysis in forensic investigations.     

Gunshot residues on dry bone after decomposition-a pilot study

Abstract: Very little literature exists concerning radiochemical and microscopic analyses of gunshot wounds in decomposed material, and even less concerning skeletonized samples; the most advanced technologies may provide useful indications for the diagnosis of suspect lesions, especially if gunshot wounds are no longer recognizable. However, we know very little of the survival of gunshot residues (GSR) in skeletonized samples. This study examined nine gunshot wounds produced on pig heads which then underwent skeletonization for 4 years, and four gunshot entries on human heads from judicial cases which were then macerated to the bone in water; the samples underwent scanning electron microscopy coupled with energy dispersive X‐ray (SEM‐EDX) analysis. Positive results for GSR were observed only in four of the nine animal samples and in all four human samples. Among the human samples, two lesions showed Pb and Sb, one lesion only Pb, and one Pb, Sb, and Ba. This pilot study showed the survival of GSR in skeletal material and therefore the crucial importance of SEM‐EDX analyses on skeletonized material. Further studies are needed in order to ascertain the role of environmental modifications of GSR.     

Characterisation of 0.22 caliber rimfire gunshot residues by time-of-flight secondary ion mass spectrometry (TOF-SIMS): a preliminary study

The application of time-of-flight secondary ion mass spectrometry (TOF-SIMS) for the characterisation of gunshot residue (GSR) from 0.22 caliber rimfire ammunition is reported. Results obtained by TOF-SIMS were compared with conventional scanning electron microscopy (SEM) studies. As could be expected, TOF-SIMS exhibited greater elemental sensitivity than SEM equipped with energy dispersive X-ray detection (SEM-EDX), and was also capable of detecting fragments characteristic of inorganic compounds. This preliminary study indicates that TOF-SIMS offers substantial potential for forensic GSR examinations as a complementary technique to SEM-EDX. In addition TOF-SIMS is applicable to the analysis of individual particles in the typical size range encountered in GSR casework.     

Detection of Gunshot Residue on Dark‐Colored Clothing Prior to Chemical Analysis

Detection of gunshot residue (GSR) is an arduous task for investigators. It is often accomplished with chemical tests, which can reveal elements and ions indicating the presence of GSR, but are likely to cause physical alteration to the pattern. In this study, the Spex Forensics Mini‐CrimeScope MCS 400, along with 16 accompanying wavelength filters, was applied to various GSR patterns and target types. Three dark shirt materials, four ammunition calibers, and eight ammunition manufacturers, along with the primer residue of the different manufacturer ammunitions were tested. Results indicate the alternate light source wavelength of 445 nm to be the optimal setting. In addition, target material plays a large role in the preservation of GSR patterns as particles burn. Furthermore, it can be extrapolated that residue, observed from a full round and firing distance of six inches, is mostly composed of unburnt gunpowder residue, not primer residue.     

Particle Analysis for the Detection of Gunshot Residue (GSR) in Nasal Samples Using Scanning Laser Ablation and Inductively Coupled Plasma-Mass Spectrometry (SLA-ICPMS)

Currently, aluminum stub with carbon adhesive devices are used to collect inorganic gunshot residues (GSR) from the hands of a shooter. In an ideal shooting case, the gunshot particles do not persist for more than 2 h in the hands of the shooter, provided that the hands have not been washed. However, for forensic analysis and inference, the extended persistence of GSR would be desirable. This study investigates a novel GSR sampling and detection protocol. Sampling was performed in the nostrils using swab devices impregnated in ethylenediaminetetraacetic acid (EDTA). The GSRs persisted for longer periods in nasal mucus than on the hands, and particles were detected 6 h after shooting occurred. The analytical determination was conducted by scanning laser ablation-inductively coupled plasma-mass spectrometry (SLA-ICPMS) which enable the identification of the number of particles and their elemental composition. Seventeen isotope signals corresponding to ¹³C, ²⁰⁵Tl and 15 analytes that are usually associated with the composition of GSR residues were monitored: ²⁷Al, ²⁹Si, ³¹P, ³³S, ³⁵Cl, ³⁹K, ⁴⁴Ca, ⁵⁷Fe, ⁶⁰Ni, ⁶³Cu, ⁶⁶Zn, ¹¹⁸Sn, ¹²¹Sb, ¹³⁷Ba, and ²⁰⁸Pb. The SLA technique enabled the reduction of the swab analysis time to 40 min. The effectiveness of this methodology was evaluated with two types of firearms: a pistol and a shotgun. The results indicated that the methodology proposed for the analysis of the nasal GSR was effective and that it can improve or complement the forensic analyses and inferences presented in a court.     

Electrical Pulse Generated Upon Discharging a Firearm and Its Implication for Gunshot Residue Analysis

Ammunition primers consisting of a mixture of lead styphnate, barium nitrate, and antimony (III) sulfide, upon deflagration, lead to the formation of inorganic gunshot residue (GSR). The cations, from their predeflagration form, undergo reduction reactions during burning to form the classic spheroidal, micron-sized particles indicative of GSR. However, the rapidly changing pressure and temperature of the reaction zone implies that the reactions cannot go to completion. In this study, we use a conductivity detector to show that GSR produces an electrical pulse which corroborates the incomplete redox chemistry. We find that the shape of some GSR formed in an electric field also suggests its nonneutral character. Tantalizingly, the formation of GSR might be a result of Coulombic repulsion shattering the molten droplets in to smaller spheroids. Lastly, we suggest that deposition or transfer of GSR could be influenced by static electricity, an area which should be further studied.     

Stubs Versus Swabs? A Comparison of Gunshot Residue Collection Techniques

Abstract: The collection efficiency of two widely used gunshot residue (GSR) collection techniques—carbon‐coated adhesive stubs and alcohol swabs—has been compared by counting the number of characteristic GSR particles collected from the firing hand of a shooter after firing one round. Samples were analyzed with both scanning electron microscopy and energy dispersive X‐rays by an experienced GSR analyst, and the number of particles on each sample containing Pb, Ba, and Sb counted. The adhesive stubs showed a greater collection efficiency as all 24 samples gave positive results for GSR particles whereas the swabs gave only positive results for half of the 24 samples. Results showed a statistically significant collection efficiency for the stub collection method and likely reasons for this are considered.     

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.     

Distribution of lead and barium in gunshot residue particles derived from 0.22 caliber rimfire ammunition.

0.22 caliber rimfire ammunition is commonly encountered in firearms incidents in Australia. This paper reports on work which has confirmed the nonhomogeneous nature of gunshot residue (GSR) particles and that the lead and barium distribution within particles varies significantly with the particle size and structure. The outcome has been an improved understanding of how the particle formation influences the ability to determine the origin of GSR derived specifically from 0.22 caliber rim fire ammunition.