Pervasiveness of inorganic gunshot residue (IGSR) in handguns after cleaning and conditioning procedures.

Memory effect in firearms that is, the possibility for a weapon to release inorganic particles whose elemental composition depends on its entire shooting history, is responsible for most of the interpretation difficulties encountered in forensic gunshot residue analysis. The presence of residues chemically inconsistent with the last discharged round, the creation of particles having unusual elemental profiles, and the dependence of residue population composition on the collection point are all manifestations of memory effect. The experimental results reported in this paper highlight the ineffectiveness of a wide number of gun cleaning procedures in reducing memory effect. Moreover, the common alternative of discharging batches of rounds having a "new" primer mixture does not fully eliminate the possibility to recover "old" residues at least from the shooter's hands. Two brand new pistols and ammunition having lead-based, leadless and heavy metal free primers were used. Specimens, collected both from the shooters' hands and from cotton targets set nearby the gun muzzle, were analyzed by SEM-EDS and by ICP-OES. After discharging 10's of new ammunitions, the number of old residues ejected from the gun muzzle indeed showed an asymptotic decrease to zero. In spite of this, the number of old residues recovered from the shooter's hands did not follow any predictable trend. These different behaviors suggest that all internal components of a gun, and not just the barrel, play a role in memory effect.

Structural segregation in GSR from mercuric primers. A preliminary study.

Since the second half of the XX century, primer mixtures based on mercury fulminate have become a rare occurrence on small ammunition markets in Western Europe and North America. As a consequence, Hg-containing gunshot residue (GSR) particles have not been as deeply investigated as residues from lead-based primer mixtures. As a matter of fact, no mention of GSR particles from mercuric primers is made by the current ASTM standard procedure for gunshot residue analysis. However, those laboratories dealing with ammunition and firearms produced in Eastern Europe or Asia still have a forensic interest in Hg-containing GSR. In this paper, a brief description of chemical composition and inner morphology of GSR particles from three different mercuric primers is reported. Regarding composition, arguments are given to promote SbSnHg residues to Characteristic of GSR particles when mercuric primers are discharged. From a morphological point of view, presence of inner nodules and other inhomogeneities were shown in GSR particles milled in a FIB/SEM. Moreover, mercury vaporization under the electron beam was observed for a particle reduced to a lamella. Mercury evanescence in GSR was interpreted in terms of mercury segregation during particle formation and higher mobility of Hg atoms in presence of defects (vacancies) in a strained lattice.

On the questioned presence of fluorine in inorganic gunshot residue. Case work experience and experimental evidences.

According to the active ASTM E1588-20 Standard Practice for Gunshot Residue (GSR) Analysis, particles from lead-based primers classified as "characteristic of GSR" will have the chemical composition lead/antimony/barium. Further elements allowed to be incorporated into GSR are explicitly listed in the ASTM guideline. Fluorine is not considered a possible additional element as no common sources of F in shooting related activities have ever been documented. Moreover, presence of fluorine was demonstrated in GSR-similar particles produced by airbag deployments and the possibility to use F as a chemical marker to exclude any discharging of a firearm was consequently suggested. In authors' case work experience, fluorine containing particles were found on stubs collected from victims' clothes, discharged firearms and shooters' hands. Adopting a "case by case" approach, a firearm-related fluorine origin was then sought. Fluorine-based protective lubricants, used both for guns and ammunition components, were experimentally confirmed as a possible source of F in GSR.

Molybdenum in Gunshot Residue: Experimental Evidences and Detection Challenges in the Presence of Lead and Sulfur.

Inorganic gunshot residue (GSR) analysis is carried out by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) in many forensic laboratories. Characteristic GSR often consists of lead­barium­antimony, commonly associated with sulfur. The strength of forensic GSR evidence increases when unusual elements are found in residues collected both from the suspect and from the discharged firearm. The presence of molybdenum in GSR, due to the use of MoS2 lubricants in firearms, is experimentally demonstrated here for the first time. The most intense molybdenum X-ray emissions are MoL peaks at 2.3 keV which overlap with PbM and SK families due to the poor resolution of EDS detectors. When Pb, S, and Mo are allegedly present in the same particle, the reliability of automatic EDS routines is at risk. Missing identifications or false detections and exclusions may then occur. Molybdenum should be considered as detected only if MoK emissions meet the peak-to-background ratio minimum requirements. A strategy to spot Mo-containing residues is described, based on the automated search of MoS2, using a new "Sulfur only" class added to the classification scheme, followed by careful manual review of all GSR particles at an acceleration voltage of 30 kV. Our proposal improves commonly adopted forensic procedures currently followed in casework.

Detecting Gunshot Residue from Sellier & Bellot Nontox Heavy Metal-free Primer by in situ Cathodoluminescence.

Gunshot residue (GSR) from the discharge of ammunition can provide crucial information in reconstructing criminal cases. Traditional primers create particles of heavy metals such as lead, barium, and antimony. In forensic laboratories, automatic inorganic particle detection is performed by scanning electron microscopy (SEM), using the backscattered electron signal to search for bright residues among the many darker environmental particles, due to higher electron density of the former. Some innovative primers, indicated as heavy metal-free (HMF), produce a residue of elements with atomic numbers below 21, urgently demanding new detecting solutions. For the first time, residues from Sellier & Bellot Nontox HMF primer are demonstrated to emit visible light under electron beam stimulation in a SEM. Cathodoluminescence is then proposed as a promising tool to both detect and characterize residues in forensic cases involving HMF primers, with minor changes to traditional analytical apparatus used for inorganic GSR analysis.

Unusual sources of Sn in GSR. An experimental study by SEM and IBA.

Gunshot Residue (GSR) produced by the discharge of a firearm often provides very useful information in criminal investigations in cases involving the use of firearms. Scanning Electron Microscopy equipped with an Energy Dispersive X-ray Spectrometer (SEM-EDS) is typically used worldwide to visualize micrometric particles constituting GSR and to analyse their elemental composition. The 2017 ASTM Standard guide for gunshot residue analysis by scanning electron microscopy/energy dispersive X-ray spectroscopy specifies that "Particles classified as characteristic of GSR will have one of the following elemental compositions: Lead, antimony, barium; Lead, barium, calcium, silicon, tin". For the first time, the presence of an additional element, such as Sn, plays a key role in ASTM particle classification. It is known that some ammunitions, used for pistols, revolvers and rifles, contain tin foil discs for sealing the primer mixture into the cup, resulting in GSR particles containing Sn. The authors faced some cases in which Sn was unexpectedly found in GSR particles from a 0.22 Long Rifle derringer and from some 12 gauge shotguns. No tin foil discs are used in rimfire ammunitions and there is no published evidence of tin foil discs in shotshell ammunitions. Following a "case by case" approach, experimental research has been carried out to explain how Sn can be present in GSR particles when the last discharged cartridge also does not contain any Sn either in components and in the explosive charges. Moreover, the use of Particle Induced X-ray Emission (PIXE) showed the capability to overcome overlap ambiguity of Sb and Sn peaks in the X-ray spectra, being a possible key issue in real shooting cases if Sn quantities are below the lower limit of SEM detection, especially when Sb is also present.

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.