Characterization of volatile organic gunshot residues in fired handgun cartridges by headspace sorptive extraction

In forensic investigation of firearm-related cases, determination of the residual amount of volatile compounds remaining inside a cartridge could be useful in estimating the time since its discharge. Published approaches are based on following the decrease of selected target compounds as a function of time by using solid phase micro-extraction (SPME). Naphthalene, as well as an unidentified decomposition product of nitrocellulose (referred to as "TEA2"), are usually employed for this purpose. However, reliability can be brought into question given their high volatility and the low reproducibility of their extracted quantities. In order to identify alternatives and therefore develop improved dating methods, an extensive study on the composition and variability of volatile residues in nine different types of cartridges was carried out. Analysis was performed using headspace sorptive extraction (HSSE), which is a more exhaustive technique compared to SPME. 166 compounds were identified (several of which for the first time), and it was observed that the final compositional characteristics of each residue were strongly dependent on its source. Variability of single identified compounds within and between different types of cartridge, as well as their evolution over time, was also studied. Many explosion products containing up to 4 aromatic rings were found to be globally present in high proportions amongst residues. 27 of them (excluding naphthalene) also presented detectable decreases during the first 24 h. Therefore, they could be used as complementary target analytes in future dating methods.

LC-MS method development and comparison of sampling materials for the analysis of organic gunshot residues

This study aimed at comparing the efficiency of various sampling materials for the collection and subsequent analysis of organic gunshot residues (OGSR). To the best of our knowledge, it is the first time that sampling devices were investigated in detail for further quantitation of OGSR by LC-MS. Seven sampling materials, namely two "swab"-type and five "stub"-type collection materials, were tested. The investigation started with the development of a simple and robust LC-MS method able to separate and quantify molecules typically found in gunpowders, such as diphenylamine or ethylcentralite. The evaluation of sampling materials was then systematically carried out by first analysing blank extracts of the materials to check for potential interferences and determining matrix effects. Based on these results, the best four materials, namely cotton buds, polyester swabs, a tape from 3M and PTFE were compared in terms of collection efficiency during shooting experiments using a set of 9 mm Luger ammunition. It was found that the tape was capable of recovering the highest amounts of OGSR. As tape-lifting is the technique currently used in routine for inorganic GSR, OGSR analysis might be implemented without modifying IGSR sampling and analysis procedure.

Measurements of gunshot residues by sector field inductively coupled plasma mass spectrometry - Further studies with pistols

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 mu g/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. (C) 2007 Elsevier B.V.. All rights reserved.

A forensic study: Lead determination in gunshot residues

Electrochemical lead analyses of gunshot residues (GSRs) were performed using an acidic solution with a bare gold microelectrode in the presence of chloride ions. GSRs from four different guns (0.38 in. revolver, 12 caliber pump-action shotgun, 0.38 repeating rifle, and a 0.22 caliber semi-automatic rifle) and six different types of ammunition (CleanRange (R), normal, semi-jacketed, especial 24g (R), 3T (R), CBC (R), and Eley (R)) were analyzed. Results obtained with the proposed methodology were compared with those from an atomic absorption spectrometry analysis, and a paired Student's t-test indicated that there was no significant difference between them at the 95% confidence level. With this methodology, a detection limit of 1.7 nmol L-1 (3 sigma/slope), a linear range between 10 and 100 nmol L-1, and a relative standard deviation of 2.5% from 10 measurements were obtained. (C) 2011 Elsevier B.V. All rights reserved.

Use of a gold microelectrode for discrimination of gunshot residues

Gunshot residues (GSR) can be used in forensic evaluations to obtain information about the type of gun and ammunition used in a crime. In this work, we present our efforts to develop a promising new method to discriminate the type of gun [four different guns were used: two handguns (0.38 revolver and 0.380 pistol) and two long-barrelled guns (12-calibre pump-action shotgun and 0.38 repeating rifle)] and ammunition (five different types: normal, semi-jacketed, full-jacketed, green, and 3T) used by a suspect. The proposed approach is based on information obtained from cyclic voltammograms recorded in solutions containing GSR collected from the hands of the shooters, using a gold microelectrode; the information was further analysed by non-supervised pattern-recognition methods [(Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA)]. In all cases (gun and ammunition discrimination), good separation among different samples in the score plots and dendrograms was achieved. (C) 2012 Elsevier B.V. All rights reserved.

Fast Detection and Chemical Characterization of Gunshot Residues by CMV-GC-MS and LIBS

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.

Measurement of airborne gunshot particles in a ballistics laboratory by sector field inductively coupled plasma mass spectrometry

The present study aimed determines lead (Pb), antimony (Sb) and barium (Ba) as the major elements present in GSR in the environmental air of the Ballistics Laboratory of the Sao Paulo Criminalistics Institute (I.C.-S.P.), Sao Paulo, SP, Brazil. Micro environmental monitors (mini samplers) were located at selected places. The PM2.5 fraction of this airborne was collected in, previously weighted filters, and analyzed by sector field inductively coupled plasma mass spectrometer (SF-HR-ICP-MS). The higher values of the airborne lead, antimony and barium, were found at the firing range (lead (Pb): 58.9 mu g/m(3); barium (Ba): 6.9 mu g/m(3); antimony (Sb): 7.3 mu g/m(3)). The mean value of the airborne in this room during 6 monitored days was Pb: 23.1 mu g/m(3); Ba: 2.2 mu g/m(3); Sb: 1.5 mu g/m(3). In the water tank room, the air did not show levels above the limits of concern. In general the airborne lead changed from day to day, but the barium and antimony remained constant. Despite of that, the obtained values suggest that the workers may be exposed to airborne lead concentration that can result in an unhealthy environment and could increase the risk of chronic intoxication. (C) 2011 Elsevier Ireland Ltd. All rights reserved.

Method development for the analysis of smokeless powders and organic gunshot residue by ultra performance liquid chromatography with tandem mass spectrometry

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.^

Química forense: perspectivas sobre novos métodos analíticos aplicados à documentoscopia, balística e drogas de abuso

In this review recent methods developed and applied to solve criminal occurences related to documentoscopy, ballistic and drugs of abuse are discussed. In documentoscopy, aging of ink writings, the sequence of line crossings and counterfeiting of documents are aspects to be solved with reproducible, fast and non-destructive methods. In ballistic, the industries are currently producing ''lead-free'' or ''nontoxic'' handgun ammunitions, so new methods of gunshot residues characterization are being presented. For drugs analysis, easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to provide a relatively simple and selective screening tool to distinguish m-CPP and amphetamines (MDMA) tablets, cocaine and LSD.

Síntese, aplicação e avaliação da toxicidade aguda de complexo orgânico à base de európio proposto como marcador fotoluminescente para a Identificação de resíduos de tiro

Um complexo de alta fotoluminescência é proposto como marcador óptico para a identificação de resíduos de tiro (GSR). O marcador é o complexo [Eu(PIC)3(NMK)3], de fórmula molecular Eu(C6H2N3O7)3.(C7H13NO)3, que apresenta o íon Eu3+ e os ligantes ácido pícrico (PIC) e n-metil-Ɛ-caprolactama (NMK). Foi realizada a caracterização quimicamente através de espectroscopia de emissão, espectroscopia de infravermelho com transformada de Fourier (FTIR), termogravimetria e análise térmica diferencial (TG/DTA), e espectrometria de massas com ionização por eletrospray e ressonância ciclotrônica de íons por transformada de Fourier (ESI-FT-ICR MS), e, em seguida, foram adicionadas diferentes massas do complexo a munições convencionais (de 2 a 50 mg por cartucho). Após os tiros, o GSR marcado foi visualmente e quimicamente detectado por irradiação UV (ʎ = 395 nm) e ESI-FT-ICR MS, respectivamente. Os resultados mostraram uma fotoluminescência eficiente e duradoura, sendo facilmente visível sobre a superfície do alvo, no ambiente, no cartucho deflagrado, na arma de fogo, e sobre as mãos e braços do atirador quando utilizada massa a partir de 25 mg do marcador em cartuchos .38 e 50 mg em cartuchos .40. Sua toxicidade aguda também foi avaliada empregando-se o Protocolo 423 da Organização para a Cooperação e Desenvolvimento Econômico (OECD) e apresentou DL50 de 1000 mg.kg-1, sendo classificado como de categoria 4 na escala do Sistema Globalmente Harmonizado de Classificação e Rotulagem de Produtos Químicos (GHS), considerado, portanto, de média toxicidade. O composto mostrou ser menos tóxico do que os componentes inorgânicos de munições convencionais (em especial o Pb), justificando o seu emprego como marcador de GSR.

Digital evidence, 'absence' of data and ambiguous patterns of reasoning

In this paper we discuss the use of digital data by the Swiss Federal Criminal Court in a recent case of attempted homicide. We use this case to examine drawbacks for the defense when the presentation of scientific evidence is partial, especially when the only perspective mentioned is that of the prosecution. We tackle this discussion at two distinct levels. First, we pursue an essentially non-technical presentation of the topic by drawing parallels between the court's summing up of the case and flawed patterns of reasoning commonly seen in other forensic disciplines, such as DNA and particle traces (e.g., gunshot residues). Then, we propose a formal analysis of the case, using elements of probability and graphical probability models, to justify our main claim that the partial presentation of digital evidence poses a risk to the administration of justice in that it keeps vital information from the defense. We will argue that such practice constitutes a violation of general principles of forensic interpretation as established by forensic science literature and current recommendations by forensic science interest groups (e.g., the European Network of Forensic Science Institutes). Finally, we posit that argument construction and analysis using formal methods can help replace digital evidence appropriately into context and thus support a sound evaluation of the evidence.

Identificação de resíduos de disparos de armas de fogo por meio da técnica de espectrometria de massas de alta resolução com fonte de plasma indutivo

The violence derived from crimes involving firearms represents one of the main concerns of society. For this reason modern techniques have emerged in forensic science to identify suspects at crime scenes. This work describes a methodology to identify residues present in the hands of suspect by using a high resolution inductively coupled plasma mass spectrometry and collection procedure based on ethylenediaminetetraacetic acid (EDTA) solution as a complexing agent in moistened swabs. In order to distinguish real gunshot residues from others types of residues present in the hand of suspect, ternary ratio per cent diagrams were developed for antimony (Sb), barium (Ba) and lead (Pb) detected on the hands of volunteers, before and immediately after shooting tests, revealing a remarkable difference in both situations.

Química forense: perspectivas sobre novos métodos analíticos aplicados à documentoscopia, balística e drogas de abuso

In this review recent methods developed and applied to solve criminal occurences related to documentoscopy, ballistic and drugs of abuse are discussed. In documentoscopy, aging of ink writings, the sequence of line crossings and counterfeiting of documents are aspects to be solved with reproducible, fast and non-destructive methods. In ballistic, the industries are currently producing ''lead-free'' or ''nontoxic'' handgun ammunitions, so new methods of gunshot residues characterization are being presented. For drugs analysis, easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to provide a relatively simple and selective screening tool to distinguish m-CPP and amphetamines (MDMA) tablets, cocaine and LSD.

Up-conversion properties of lanthanide-organic frameworks and how to track ammunitions using these materials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Desenvolvimento de métodos analíticos limpos para determinações forenses: chumbo em resíduos de disparo e furosemida em doping

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)