Raman hyperspectral imaging in conjunction with independent component analysis as a forensic tool for explosive analysis: the case of an ATM explosion

In this work, Raman hyperspectral imaging, in conjunction with independent component analysis, was employed as an analytical methodology to detect an ammonium nitrate fuel oil (ANFO) explosive in banknotes after an ATM explosion experiment. The proposed methodology allows for the identification of the ANFO explosive without sample preparation or destroying the sample, at quantities as small as 70 μg cm−2. The explosive was identified following ICA data decomposition by the characteristic nitrate band at 1044 cm−1. The use of Raman hyperspectral imaging and independent component analysis shows great potential for identifying forensic samples by providing chemical and spatial information.174628632CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPSem informação573672/2008-308/57805-

Direct detection of triacetone triperoxide (TATP) in real banknotes from ATM explosion by EASI‐MS

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)In Brazil, automated teller machine (ATM) has become a major target of theft incursions toward explosion. Efficient analysis of explosives residues on suspect banknotes is a serious issue in forensic labs, and guide to the crime solution. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to be a simple and selective screening tool to identify peroxide explosives on real banknotes collected from ATM explosion. Analyses were carried out directly on the banknotes surfaces without any sample preparation, identifying triacetone triperoxide (TATP) and diacetone diperoxide (DADP). Homemade EASI source was coupled to ultrahigh-resolution and ultrahigh accuracy FT-ICR MS and revealed the ion of m/z 245 correspondent to sodiated TATP [C9H18O6Na](+) and the ion of m/z 171 related to sodiated DADP [C6H12O4Na](+), ions that is the sodiated DADP and the ions of m/z 173 and 189 related to [C6H14O4Na](+) and [C6H14O4K](+), respectively, which are associated to chemical markers of TATP domestic route synthesis. EASI source coupled to a single quadrupole mass spectrometer provides an intelligent and simple way to identify the explosives TATP, DADP and its domestic synthesis markers.In Brazil, automated teller machine (ATM) has become a major target of theft incursions toward explosion. Efficient analysis of explosives residues on suspect banknotes is a serious issue in forensic labs, and guide to the crime solution. Easy ambient son424370375CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)23038.006844/2014–4

Anti-theft device staining on banknotes detected by mass spectrometry imaging

We describe the identification and limits of detection of ink staining by mass spectrometry imaging (MSI), as used in anti-theft devices (ATDs). Such ink staining is applied to banknotes during automated teller machine (ATM) explosions. Desorption electrospray ionization (DESI) coupled with high-resolution and high-accuracy orbitrap mass spectrometry (MS) and a moving stage device were applied to obtain 2D molecular images of the major dyes used for staining, that is, 1-methylaminoanthraquinone (MAAQ), rhodamine B (RB) and rhodamine 6G (R6G). MAAQ could not be detected because of its inefficient desorption by DESI from the banknote cellulose surface. By contrast, ATD staining on banknotes is perceptible by the human naked eye only at concentrations higher than 0.2μgcm(-2), whereas both RB and R6G at concentrations 200 times lower (as low as 0.001μgcm(-2)) could be easily detected and imaged by DESI-MSI, with selective and specific identification of each analyte and their spatial distribution on samples from suspects. This technique is non-destructive, and no sample preparation is required, which ensures sample preservation for further forensic investigations.We describe the identification and limits of detection of ink staining by mass spectrometry imaging (MSI), as used in anti-theft devices (ATDs). Such ink staining is applied to banknotes during automated teller machine (ATM) explosions. Desorption electro2602226CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR23038.006844/2014-4

Forensic application of X-ray fluorescence spectroscopy for the discrimination of authentic and counterfeit revenue stamps

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Energy-dispersive X-ray fluorescence (ED-XRF) spectroscopy with data treatment via chemometric tools was explored as an analytical protocol to discriminate between authentic and counterfeit revenue stamps. Untreated samples were directly analyzed, and the discrimination was based on the characterization of constituent elements present in the inks and paper. Authentic samples and samples that were suspected of being counterfeit were analyzed at three different areas on their surfaces: the ink-printed area, the non-printed area, and the holographic area. Principal component analysis (PCA) was applied to the data to discriminate between authentic and counterfeit revenue stamps. Major differences in the elemental composition were noted (according to chemometrics and t-test, p < 0.05), and ED-XRF spectroscopy plus PCA protocol is proposed for use by non-specialist operators to screen for counterfeit stamps.Energy-dispersive X-ray fluorescence (ED-XRF) spectroscopy with data treatment via chemometric tools was explored as an analytical protocol to discriminate between authentic and counterfeit revenue stamps. Untreated samples were directly analyzed, and the701119101915CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)23038.006844/2014-46This work was supported by CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (grant number 23038.006844/2014-46

Characterization Of Anti-theft Devices Directly From The Surface Of Banknotes Via Easy Ambient Sonic Spray Ionization Mass Spectrometry.

Using Brazilian banknotes as a test case, forensic examination and identification of Rhodamine B dye anti-theft device (ATD) staining on banknotes were performed. Easy ambient sonic spray ionization mass spectrometry (EASI-MS) was used since it allows fast and simple analysis with no sample preparation providing molecular screening of the surface with direct desorption and ionization of the security dye. For a more accurate molecular characterization of the ATD dye, Q Exactive Orbitrap™ Fourier transform (tandem) mass spectrometry using eletrospray ionization (ESI-HRMS/MS) was also applied.55285-29

Characterization Of Anfo Explosive By High Accuracy Esi(±)-ftms With Forensic Identification On Real Samples By Easi(-)-ms.

Ammonium nitrate fuel oil (ANFO) is an explosive used in many civil applications. In Brazil, ANFO has unfortunately also been used in criminal attacks, mainly in automated teller machine (ATM) explosions. In this paper, we describe a detailed characterization of the ANFO composition and its two main constituents (diesel and a nitrate explosive) using high resolution and accuracy mass spectrometry performed on an FT-ICR-mass spectrometer with electrospray ionization (ESI(±)-FTMS) in both the positive and negative ion modes. Via ESI(-)-MS, an ion marker for ANFO was characterized. Using a direct and simple ambient desorption/ionization technique, i.e., easy ambient sonic-spray ionization mass spectrometry (EASI-MS), in a simpler, lower accuracy but robust single quadrupole mass spectrometer, the ANFO ion marker was directly detected from the surface of banknotes collected from ATM explosion theft.249C156-16