A Study of Background Levels of Antimony,Barium, and Lead on Vehicle Surface Samples by Graphite Furnace Atomic Absorption

Law enforcement agencies routinely sample for gunshot residue (GSR) by bulk techniques and often submit swabs taken from other surfaces besides the hands of the suspect shooter. This study aims to establish the prevalence of antimony, barium, and lead on normally handled automobile surfaces by graphite furnace atomic absorption analysis. No positives were determined on 50 sampled automobile surfaces above cutoff (positive) from background levels. Transfers of GSR particles from shooter hands to automobile surfaces were found to potentially allow for positive GSR determinations, but such transfers seem to be dependent on the shooting conditions and length of GSR exposure. We determined that our bulk analysis method yields an overall 87.94 ± 5.52% extraction efficiency from cotton swabs, while the LOQ determinations strengthening the fact that bulk analysis methods are valid and valuable tools for GSR investigations.     

Analysis of gunshot residue test results in 112 suicides

The results of gunshot residue (GSR) tests in 112 suicide cases investigated by the U.S. Army Criminal Investigation Command over a ten-year period are described. Only suicide cases in which there was certainty that the victim fired a weapon were examined in an effort to reduce ambiguous results. Previous case work research by Rudzitis indicated that positive GSR test results were encountered in suicides 62% of the time using various combinations of neutron activation analysis (NAA) and atomic absorption spectrophotometry (AAS). Threshold values of 0.2-micrograms antimony and 0.3-micrograms barium (0.2-micrograms antimony and 0.5-micrograms barium after 1985) used by the U.S. Army Criminal Investigation Laboratory resulted in positive GSR results in suicide cases 38% of the time. The effects of time, location of body, handling of the body, weapon type, caliber, and condition of the hands on GSR results are examined. Case studies involving suicides by unit armorers are discussed.     

A preliminary investigation into the use of FTIR microscopy as a probe for the identification of bullet entrance holes and the distance of firing

FTIR spectroscopy has been found to be a valuable probe for the analysis of the distribution of organic components such as nitroglycerine in gunshot residues deposited on and around the bullet entrance hole of the clothing of the victim in short range firearm discharges. The method can be utilised for the detection and estimation of organic gunshot residues (OGSR) on the hands and clothing of the shooter. The method is specific and sensitive and is likely to be free from interference from, for example, environmental pollution. The method shows potential to be utilised as a suitable alternative to the widely used SEM-EDX analysis of the total contents of lead, barium and antimony present in the gunshot deposits around the bullet entrance hole. The method was tested in the laboratory and the results were validated by Gas Chromatography-Mass Spectrometry (GC-MS).     

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.     

Close proximity gunshot residues

Intuitively, a hand held in close proximity to a firearm at the instant of discharge will intercept a significant amount of gunshot residue, even though the hand did not actually come into contact with the weapon. There is, however, little information specifically described in the forensic science literature concerning the residue levels which might be encountered in such an instance. The present work confirms that antimony levels consistent with an individual having fired or handled a firearm may be intercepted by a hand held in close proximity.     

常见洗手方式对92式手枪射击残留物检出率的影响

目的研究常见洗手方式对92式手枪射击残留物检出率的影响,为确定犯罪嫌疑人射击与否的推断提供依据。方法实验人员使用92式手枪分别射击1枪和3枪,射击后0．5h内,射击人员的手分别用清水、肥皂和洗手液清洗3遍（对照组为未清洗）,对实验人员的手部进行射击残留物的提取,利用扫描电镜和能谱仪对射击残留物进行检验。结果持枪射击后,射击人的手部会附着大量的射击残留物,用常见的洗手方式进行清洗后,仍然能检测到射击残留物,且不同的洗手方式对射击残留物的检出率的影响差异显著。结论常见洗手方式不能完全清除手部的射击残留物,对涉枪案件犯罪嫌疑人的判定有一定的参考价值。     

Blood-spatter patterns: hands hold clues for the forensic reconstruction of the sequence of events

Biologic and nonbiologic traces on the hands are of particular importance for the forensic reconstruction of shooting incidents; gunpowder residue analysis in particular helps determine whether the gunshot is close range or distant. In crime scene investigation, knowledge about the morphology of bloodstain patterns-including gunshot-related back spatter-has increased since various experimental examinations have been performed in the last years; nowadays, these traces are frequently used for forensic crime scene reconstruction. The goal of this study was to deduce the position and orientation of the hands, and therefore the firearm, according to the bloodstain patterns on the hands of the deceased. For this purpose blood-spatter stains on the hands were examined on site in 5 suicides caused by gunshot. In all cases, forensically relevant conclusions regarding forensic reconstruction were enabled through close examination of the spatter marks. Therefore, in shooting incidents, analysis and documentation of blood-spatter findings on the hands is recommended before hands are tested for gunpowder residue or wrapped for the transport of the body.     

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.     

Forensic veterinary radiology: ballistic-radiological 3D computertomographic reconstruction of an illegal lynx shooting in Switzerland

The most popular handgun in Brazil is the single round-barrel caliber 0.38 revolver. In recent years, however, owing to the modernization of police arms and their availability on the legal and illicit markets, pistols have become increasingly popular and currently represent about 20% of police seizures. In a previous paper we presented a novel collection method for gunshot residues (GSR) using a sampling procedure based on ethylenediamine-tetraacetic acid (EDTA) solution as a complexing agent on moistened swabs with subsequent detection using sector field-high resolution-inductively coupled plasma-mass spectrometry (SF-HR-ICP-MS). In the present paper, we discuss the capability of this methodology to identify antimony (Sb), barium (Ba) and lead (Pb) on the hands of volunteers after shot tests with 9 mm and 0.40 in. caliber pistols. Two types of munitions were tested: 9 mm Taurus and clean range. The use of a technique with high sensitivity, such as SF-HR-ICP-MS, permits the identification of low concentrations (less than 1 microg/L) of metals in firearm residue and constitutes a powerful tool in forensic science. We also discuss the importance of the sampling procedure, including collection from a different body part than the gun hand of the suspect. Comparison of the analytical data obtained allows clear discrimination between samples from the hands of shooters and non-shooters.     

Variation of the chemical contents and morphology of gunshot residue in the surroundings of the shooting pistol as a potential contribution to a shooting incidence reconstruction

A study of the chemical contents and sizes of gunshot residue originating from 9×18mm PM ammunition, depositing in the vicinity of the shooting person was performed by means of scanning electron microscopy and energy dispersive X-ray spectrometry. Samples of the residue were collected from targets placed at various distances in the range 0-100cm as well as from hands and clothing of the shooting person. Targets were covered by fragments of white cotton fabric or black bovine leather. In the case of cotton targets microtraces were collected from circles of 5 and 10cm in radius. Results of the examinations in the form of numbers of particles, proportions of their chemical classes and dimensions revealed a dependence on the distance from the gun muzzle, both in the direction of shooting and in the opposite one, i.e., on the shooting person. The parameters describing gunshot residue differed also depending on the kind of the target substrate. The kind of obtained information gives rise to understanding the general rules of the dispersion of gunshot residue in the surroundings of the shooting gun. Thus, it may be utilised in the reconstruction of shooting incidences, especially in establishing the mutual positions of the shooter and other participants of the incident.     

Gunshot residue testing in suicides: Part I: Analysis by scanning electron microscopy with energy-dispersive X-ray

Several different methods can be employed to test for gunshot residue (GSR) on a deceased person's hands, including scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM-EDX) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Each of these techniques has been extensively studied, especially on living individuals. The current studies (Part I and Part II) were designed to compare the use and utility of the different GSR testing techniques in a medical examiner setting. In Part I, the hands of deceased persons who died from undisputed suicidal handgun wounds were tested for GSR by SEM-EDX over a 4-year period. A total of 116 cases were studied and analyzed for caliber of weapon, proximity of wound, and results of GSR testing, including spatial deposition upon the hands. It was found that in only 50% of cases with a known self-inflicted gunshot wound was SEM-EDX positive for at least 1 specific particle for GSR. In 18% of the cases there was a discernible pattern (spatial distribution) of the particles on the hand such that the manner in which the weapon was held could be determined. Since only 50% of cases where the person is known to have fired a weapon immediately prior to death were positive for GSR by SEM-EDX, this test should not be relied upon to determine whether a deceased individual has discharged a firearm. Furthermore, in only 18% of cases was a discernible pattern present indicating how the firearm was held. The low sensitivity, along with the low percentage of cases with a discernible pattern, limits the usefulness of GSR test results by SEM-EDX in differentiating self-inflicted from non-self-inflicted wounds.     

Identification of gunshot residue: a critical review

A review of the scientific papers published on inorganic gunshot residue (GSR) analysis permits to study how the particle analysis has shown its capability in detection and identification of gunshot residue. The scanning electron microscope can be the most powerful tool for forensic scientists to determine the proximity to a discharging firearm and/or the contact with a surface exposed to GSR. Particle analysis can identify individual gunshot residue particles through both morphological and elemental characteristics. When particles are detected on the collected sample, the analytical results can be interpreted following rules of a formal general interpretative system, to determine whether they come from the explosion of a primer or from other possible sources. The particles on the sample are compared with an abstract idea of "unique" GSR particle produced by the sole source of the explosion of a primer. "Uniqueness" is not the only problem related to GSR detection and identification for a forensic scientist. With "not-unique" particles interpretation of results is extremely important. The evidential strength of "not-unique" particles can increase with a more fruitful interpretative framework based on Bayes rule. For the assessment of the value of a GSR in linking a suspect and a crime, it is important to compare two hypothesis: the first can be that of the evidence if the suspect has been shooting in a specific situation, the second that of the evidence if the suspect was not involved in this shooting. This case specific or case-by-case approach is closer to what the court is interested in. The authors consider that a "case-by-case" approach should be followed whenever possible. Research of models and data such as those developed in other trace evidence material (fibres, glass, etc.) using a Bayesian approach is suggested in the interpretation of GSR.     

Observations and statistics relating to suicide weapons

The weapon at the scene of a suicide provides a resource in addressing such questions as frequency of blood in or on the weapon, location of the weapon with respect to the body, and evidence of firearm discharge residues on the hand. The first 195 weapons were tested for blood by a technique different from the following 202 weapons. Results were obtained which caused procedural changes in blood detection. Data are presented for frequency of blood in and on the muzzle of weapons, relative frequency of location of suicidal gunshot wound, and percent "positive" findings of gunshot residue metals on the hands. It was found that suicidal gunshot wounds were 3 times more frequent to the head than the chest, and that no significant difference was noted between males and females in this study. Scene photographs reveal that the suicide weapon is in or resting on the hand of the decedent 20% of the time with handguns and 11% of the time with long guns.     

Gunshot residue in Chicago police vehicles and facilities: an empirical study

Suspects in shooting investigations in Chicago are routinely transported in department vehicles and detained in department facilities prior to gunshot residue (GSR) evidence collection. The GSR test results are used to associate the suspect with primary exposure to GSR. The potential for these vehicles and facilities being sources of secondary GSR contamination needed to be determined. A total of 201 samples were collected from randomly selected vehicles and detention facilities. The sampling collected trace materials from surfaces that suspects' hands may contact during the arrest process. These samples were examined for the presence of GSR particles using scanning electron microscopy. Upon completion of the automated analysis, those particles that met an initial GSR screening criterion were relocated and reanalyzed. The locations where GSR particles were recovered allowed us to make recommendations to the Chicago Police Department with regard to transporting and detaining these suspects. The low number of GSR particles recovered suggests that the potential for secondary contamination, although present, is relatively low.     

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.     

Detection of Gunshot Residue in Blowfly Larvae and Decomposing Porcine Tissue Using Inductively Coupled Plasma Mass Spectrometry (ICP‐MS)*

Abstract: Blowfly larvae and porcine tissue contaminated with gunshot residue (GSR) were collected during summer and winter months, over a 37‐day and a 60‐day sampling period, respectively. Wound samples were microwave‐digested and analyzed by inductively coupled plasma mass spectrometry (ICP‐MS) for the detection of antimony, barium, and lead. During summer, the 37‐day sampling period encompassed all stages of decomposition, except skeletonization. The three elements were detected in larvae only on days 3 and 4 after death but were detected at significant levels in tissue samples throughout the entire sampling period. In winter, no significant decomposition was observed throughout the 60‐day sampling. Although temperatures were too low for blowfly activity, the three elements were detected in the tissue samples at relatively constant, significant levels. Hence, GSR determination in tissue was more dependent on decomposition stage rather than time since death.     

The application of anodic stripping voltammetry to forensic science I. The construction of a low-cost polarograph

Intended for forensic gunshot residue analyses and other applications, a low-cost (about $250.00) polarograph was constructed. This instrument is essentially' an operational amplifier version of a three-electrode potentiostat containing a voltage ramp generator, a scan amplifier, an amplifier and a current-to-voltage converter, two voltage followers and an electrolysis cell. An anodic stripping procedure was developed for the simultaneous determination of a zinc, cadmium, lead, antimony and copper mixture, and used for testing the instrument. Effects of pre-electrolysis time, concentration changes, presence of other species and overlapping were also studied.     

Evaluation of the Simultaneous Analysis of Organic and Inorganic Gunshot Residues Within a Large Population Data Set Using Electrochemical Sensors*,†

The increasing demand for rapid methods to identify both inorganic and organic gunshot residues (IGSR and OGSR) makes electrochemical methods, an attractive screening tool to modernize current practice. Our research group has previously demonstrated that electrochemical screening of GSR samples delivers a simple, inexpensive, and sensitive analytical solution that is capable of detecting IGSR and OGSR in less than 10 min per sample. In this study, we expand our previous work by increasing the number of GSR markers and applying machine learning classifiers to the interpretation of a larger population data set. Utilizing bare screen-printed carbon electrodes, the detection and resolution of seven markers (IGSR; lead, antimony, and copper, and OGSR; nitroglycerin, 2,4-dinitrotoluene, diphenylamine, and ethyl centralite) was achieved with limits of detection (LODs) below 1 µg/mL. A large population data set was obtained from 395 authentic shooter samples and 350 background samples. Various statistical methods and machine learning algorithms, including critical thresholds (CT), naïve Bayes (NB), logistic regression (LR), and neural networks (NN), were utilized to calculate the performance and error rates. Neural networks proved to be the best predictor when assessing the dichotomous question of detection of GSR on the hands of shooter versus nonshooter groups. Accuracies for the studied population were 81.8 % (CT), 88.1% (NB), 94.7% (LR), and 95.4% (NN), respectively. The ability to detect both IGSR and OGSR simultaneously provides a selective testing platform for gunshot residues that can provide a powerful field-testing technique and assist with decisions in case management.     

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.     

Automated SEM/EDS Analysis of Airbag Residue.* I: Particle Identification

Abstract: Deployed airbags can be a valuable source of probative forensic materials. During an accident, trace evidence can be deposited on the airbag cover and in addition, the residue produced by the gas generation system is released into the passenger compartment of the vehicle as the airbag deflates. This residue can be used to associate a suspect with the vehicle at the time of the accident. This study identifies particles containing zirconium, strontium, and/or copper–cobalt along with other elements from the gas generation systems and aluminum silicon microfibers from airbag filters as the probative material which may be produced and deposited on a suspect’s hands and/or clothing. Scanning electron microscopy can be used to identify this metallic residue. Modification of the search criterion used for gunshot residue analysis allows for automated analysis of the samples. Proper collection of the airbag standard is essential to identify which materials were produced. Prompt collection of suspect samples allows the analysts the ability to make the proper identifications and associations. This analytical technique can be a probative tool in criminal investigations.