RESUMO

The automated search software integrated with a scanning electron microscope (SEM/EDS) has been the standard tool for detecting inorganic gunshot residues (iGSR) for several decades. The detection of these particles depends on various factors such as collection, preservation, contamination with organic matter, and the method for sample analysis. This article focuses on the influence of equipment resolution setup on the backscattered electron images of the sample. The pixel size of these images plays a crucial role in determining the detectability of iGSR particles, especially those with sizes close to the pixel size. In this study, we calculated the probability of missing all characteristic iGSR particles in a sample using an SEM/EDS automated search and how it depends on the image pixel resolution setup. We developed and validated an iGSR particle detection model that links particle size with equipment registers and applied it to 320 samples analyzed by a forensic science laboratory. Our results show that the probability of missing all characteristic iGSR particles due to their size is below 5% for pixel sizes below 0.32 µm2 . These findings indicate that pixel sizes as large as twice the one commonly used in laboratory casework, that is, 0.16 µm2 , are effective for initial sample scanning, yielding good detection rates of characteristic particles that could exponentially reduce laboratory workload.

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Currently, SEM-EDS is used to detect gunshot residue (GSR) from the presence of Ba, Pb, and Sb in the sample. However, the development of new nontoxic ammunition (NTA) has prevented conventional metals from being found. In this work, we aim to determine the presence of an inorganic luminescent chemical marker based on rare earth in gunshot residues using the technique of squarewave voltammetry (SWV). After firing, the luminescent complex [(Eu2 Zr)(btc)3 (Hbtc)0.5 .6H2 O], which is used as a chemical marker, can be detected under a UV lamp. An aqueous solution with 0.1 mol L-1 KCl as supporting electrolyte can be easily collected on carbon paste electrode surfaces for SWV analysis A = 100 mV, f = 10 Hz, and step potential of 5 mV are required. The luminescent marker incorporated into the carbon paste electrode showed two anodic peak currents in the region of 0.4 V (vs Ag/AgCl) and at 0.75 V (vs Ag/AgCl) and also a cathodic one in 0.4 V (vs Ag/AgCl). SEM-EDS was able to analyze the same voltammetric results for conventional and nontoxic ammunition containing the luminescent marker. Therefore, voltammetry and SEM-EDS are valid for detecting the new residue marker in GSR. Despite this, the electrochemical method is still more advantageous because of its low cost and lack of expensive equipment and supplies in forensic laboratories.

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Entomotoxicology allows the detection and analysis of substances such as poisons, drugs, and metals in necrophagous insects using analytical protocols. In a forensic situation related to death by gunshot, the gunshot residue (GSR) is dispersed at the crime scene and may be consumed by necrophagous insects. Lead (Pb) is the most abundant metal in GSR samples and it can be determined using non-portable methods. However, the toxicity effects of GSR samples on Lucilia cuprina (Diptera: Calliphoridae) and the detection of Pb via portable electrochemical methods have not been investigated. This study describes for the first time the toxicity analysis of Pb on immature L. cuprina through their survival rate and influence of Pb on immature development. In addition, the bioaccumulation of Pb in the larvae samples was determined based on square wave anodic stripping voltammetry (SWASV) measurements. The results revealed a low limit of detection to Pb (6.5 µg L-1) and the analytical performance was satisfactory because it measures Pb levels in larvae exposed to a diet containing 50 µg Pb g-1. Furthermore, the levels of Pb influenced the survival rate and development time of the immature L. cuprina. Larvae exposed to a high concentration of the metal (50 µg Pb g -1) showed statistically significant changes (p < 0.05). The presence of Pb in immature L. cuprina can be used to estimate the post-mortem interval; thus, the present study provides important information in forensic entomology.

Assuntos

RESUMO

3D-printing is an emerging technique that enables the fast prototyping of multiple-use devices. Herein we report the fabrication of a 3D-printed graphene/polylactic acid (G-PLA) conductive electrode that works as a sampler and a voltammetric sensor of metals in gunshot residue (GSR) using a commercially-available G/-PLA filament. The 3D-printed surface was used as swab to collect GSR and next submitted to a square-wave voltammetric scan for the simultaneous detection of Pb2+ and Sb3+. The proposed sensor presented excellent analytical performance, with limit of detection values of 0.5 and 1.8 µg L-1 to Pb2+ and Sb3+, respectively, and linear ranges between 50 and 1500 µg L-1. Sampling was performed through the direct contact of G-PLA electrode in hands and clothes of shooters, followed by immersion in the electrochemical cell in the presence of supporting electrolyte for the SWASV scan. The proposed method showed a great performance in the recovery, identification and semi-quantification of Pb2+ and Sb3+ in the evaluated samples without the need for sample preparation. Moreover, the device can be reused as sampler and sensor (until three times without loss of electrochemical performance) and the fabrication is reproducible (RSD = 7%, for three different devices). Hence, this 3D-printed material is an excellent candidate for the analysis of GSR, an indispensable analysis in the forensic field.

Assuntos

RESUMO

The concentrations of lead (Pb), barium (Ba), and antimony (Sb), characteristic of GSR, were determined in soil sediments and immature (larvae) of cadaveric flies of the family Calliphoridae, by inductively coupled plasma mass spectrometry (ICP-MS). This research refers to a case study from two real crime scenes in which the corpses were in an advanced state of decomposition. In case 1, the victim had holes similar to gunshot wounds, and in case 2, there was no evidence of perforations in the corpse. Soil sediment collection was performed at three different points of the terrain, at a minimum distance of 10 m from the corpse, for cases 1 and 2. In relation to the collection of immatures, larvae were collected in regions of the mouth, nose, and orifices similar to the entry of firearms projectile into the body, for case 1, and collection of larvae and pupae, located on the body and underneath it, for case 2. It was possible to detect and quantify the three elements of interest (Pb, Ba, and Sb) by ICP-MS in both sediment and cadaveric larvae. Concentrations of 4.44, 8.74, and 0.08 µg/g were obtained for Pb, Ba, and Sb, respectively, in the soil for case 1. For the case 2, the concentrations in Pb, Ba, and Sb were from 16.34 to 26.02 µg/g; from 32.64 to 57.97 µg/g and from 0.042 to 0.30 µg/g, respectively. In the larvae, Pb, Ba, and Sb were quantified in cases 1 and 2 with a concentration of 6.28 and 1.78 µg/g for Pb, 1.49 and 2.94 µg/g for Ba, 0.50 µg/g and

Assuntos

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The metal-organic framework (MOF) [Eu(DPA)(HDPA)] (where DPA is dipicolinic acid) has been previously reported as an efficient marker for gunshot residues (GSRs). Since this marker will be in contact with various shooters, industrial workers, and the environment, however, it is important to identify its toxicity. In this work, the oral and the inhalation acute toxicities of the MOF [Eu(DPA)(HDPA)] (also called R-Marker) were evaluated in young Wistar rats using Guidelines 423 (oral) and 436 (inhalation) from the Organisation for Economic Co-operation and Development (OECD). Animal behavior; body weight, water, and food intake; and organ weight, as well as biochemical parameters were evaluated in both evaluations. For the inhalation test, a concentration of 1 mg·Lair-1·(4 h-1) was reached in a whole-body inhalation chamber. When the respiratory tract was analyzed, it was observed that part of the marker had been swallowed instead of inhaled by the animal. For the oral test, the highest administrated dose was 2000 mg/kg with no sign of toxicity. This marker has been classified in the least toxic category of the Globally Harmonized System (GHS; category 5), with an oral median lethal dose (LD50) of 5000 mg/kg. After the oral administration, the feces of the animals were collected using a metabolic cage. Luminescent feces were present up to 24 h after administration, indicating that the marker had been excreted by the organism without causing intoxication. This study has opened perspectives for drug delivery and toxicity studies, since it enables visual detection of the marker.

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The collection of gunshot residue on fabric can be an arduous task due to the microscopic size of particles (blind collection) and sheddability of some fabrics. The introduction of luminescent markers and consequent formation of luminescent gunshot residue (LGSR) can facilitate this analysis. In this study, different fabrics were analyzed in order to verify the persistence of the LGSR on them, the possibility of collecting and analyzing particles by video spectral comparator (VSC) and SEM/EDS. Also, different colored fabrics were used as targets in order to investigate influence of fabric color on LGSR visualization. Furthermore, the influence of the fabric type in the distribution of the LGSR deposited around the projectile´s hole entrance was evaluated. The fabric sheddability did not alter collection of the particles or analysis. It was possible to observe and collect LGSR on all tested fabrics, even after the fabric had been shaken, or in colored fabrics.

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Currently the great majority of the criminal acts have involved the use of firearms, for these reasons the evidences generate from these are one of the fundamental pillars of a forensic investigation. The firearm leaves evidence known as gunshot residue (GSR), which is principally composed of burnt and unburnt particles from the detonation, as well as fragments of the bullet, cartridge case, and the firearm. Gunshot residue (GSR) is produced when a firearm is discharged and large quantities of it can be transferred to an individual who has fired. SEM-EDX is the common technique used in the forensic laboratories, the analysis consists in detecting the particles and its elements. In this work we propose the use of X-ray Spectrometry by Total Reflection (TXRF) for the analysis of metals present in related samples in ballistic cases. The analysis was focused in the relationship of three elements present in GSR. A series of experiments with different persons firing gun of 9 mm was performed in a shooting range. Analytical XRFS signals corresponding to K line of Copper and L lines Barium and Lead were employed as the best discriminating variables. Machine Learning techniques, such as discriminant analysis, supported vector machines and partial least squares - discriminant analysis, enable the correct classification of all samples analyzed. A hundred samples were analyzed so far, this method has demonstrated a very high classification performance for detecting gunpowder residues in the skin.

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Gunshot residues (GSR) are important physical evidence in firearm-related crimes. Recently developed non-toxic ammunition, however, requires a new methodology for its characterization. To overcome this drawback, the introduction of noncommercial luminescent markers in ammunition was proposed. These markers, synthesized and added to the gunpowder, presented as a versatile tool for GSR analysis, since they require UV radiation alone to visualize the luminescent GSR (LGSR). This has opened up new perspectives for understanding GSR behavior at a crime scene. This work aims to expand previous studies performed with the luminescent markers in forensic contexts, exploring four different important aspects related to GSR behavior. Using LGSR amount/dispersion and a series of blind tests with marked ammunition, we tried to (1) identify the shooter position; (2) estimate the shooting distance; (3) evaluate the influence of the pistol type on the LGSR distribution on the shooter's hands and guns; and (4) study the transference of LGSR by a chain of handshaking. For this purpose, a portable UV lamp (λ=254nm) and/or techniques such as video spectral comparator (VSC) and scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDS) were used to visualize and analyze the residues. As a result, the observation of the LGSR enabled accurate determination of the shooter position and the firing distance without any chemicals. Besides, the LGSR were visualized on different kinds of pistols, regardless of firing mechanism. And finally, this study evidenced transference of residues from shaking hands with the shooter, which should be carefully considered when interpreting the results of a GSR analysis.

RESUMO

Gunshot residues (GSR) from a total of nine different caliber ammunitions produced in Brazil were analyzed and characterized by transmission (TEM) and scanning electron microscopy (SEM). GSR particles are composed of spherical particles of several micrometers of diameter containing distinct amounts of lead, barium and antimony, along with other organic and inorganic elements arising from the primer, gunpowder, the gun and the bullet itself. This study was carried out to obtain additional information on the properties of GSR nanoparticles originated from different types of regular ammunition produced in Brazil by CBC. Besides the SEM, we have used a TEM, exploring its high magnification capability and ability to explore internal structure and chemical composition of submicron particles. We observed that CBC ammunition generated smaller particles than usually reported for other ammunitions and that the three component particles are not a majority. TEM analysis revealed that GSR are partially composed of sub-micron particles as well. The electron diffraction pattern from these particles confirmed them to be mainly composed of lead oxides crystalline nanoparticles that may be agglomerated into larger particles. Energy dispersive X-ray spectroscopy revealed that most of them were composed of two elements, especially PbSb. Ba was not a common element found in the nanoparticles.