A preliminary study of fingerprint aging using near infrared hyperspectral imaging (NIR-HSI).

Fingerprinting is one of the most commonly used techniques to obtain pieces of evidence for identification of individuals. An estimation of how long a trace has been left at a crime scene could represent an important improvement for criminal investigations. There is no reliable analytical method, however, to estimate the age of a fingerprint, since this is an uncontrolled process and changes are affected by factors such as environmental conditions. This study aims to better understand the aging process of fingerprints and identify the relevant variables and limitations of the fingerprint aging process using near infrared hyperspectral imaging (NIR-HSI). For this purpose, aging of the fingerprints of 13 volunteers was evaluated using partial least squares - discriminant analysis (PLS-DA) as a preliminary exploratory approach. Four different modelling approaches were evaluated. The percentage of correctly classified pixels varied from 20.92% to 66.67%. An analysis of the associated spectra found that during the first days of aging the degradation of fat-soluble components, as well as the elimination/absorption of water, seemed to follow non-uniform trends and vary in degradation rate from donor to donor. Better classification tended to occur over longer aging times.

Luminescent Marker for GSR: Evaluation of the Acute Oral and Inhalation Toxicity of the MOF [Eu(DPA)(HDPA)].

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.

Analysis of Luminescent Gunshot Residue (LGSR) on Different Types of Fabrics.

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.

Evaluation of interferers in sampling materials used in explosive residue analysis by ion chromatography.

Analysis of explosive residues is of special interest in forensic science. It can be crucial for investigating acts of terrorism or robberies. Ion Chromatography (IC) is a standard technique used by many forensic labs in these cases. Due to the common nature of many explosives and the inherent dirtiness of samples from explosion scenes, sometimes inconclusive or false positive results are obtained by IC, making the identification of interferers extremely important. One possible source of interferer can be the sampling materials themselves, as investigated in this work. First of all, interferers from forensic swabs and syringe filters were evaluated, as these are commonly employed in explosive residue IC analysis. Among the 6 tested samples, only two syringe filters were considered free of interferers. Significant amounts (>0.2mg/L) of Na+, K+, Mg2+, Ca2+, Cl-, and SO42- were found in all forensic swabs and two syringe filters. Then, some ordinary commercial materials, such as cotton swabs, cotton balls, and cotton discs were also tested, as they are often employed in a forensic routine, also. These also showed significant amounts (>0.2mg/L) of Na+, K+, Cl-, NO3-, and SO42-. However, the total concentration of interferers in ordinary commercial materials was lower than in the forensic swabs. Then the effectiveness of removing interferers by washing sampling (swabs, and cotton balls, rolls and disk) and pre-processing (syringe filters) materials was evaluated. This revealed that the interferers could be removed with at least three washes. The results indicated that the sampling materials used for explosion scene analysis should be carefully addressed in forensic analysis. First, by making a previous analysis of the sampling material, preferably prior to use, to evaluate the presence of interferers to ensure that only material free of interferers is used. When it is not possible to perform a prior analysis of sampling materials, they should be analyzed concomitantly with the samples from the post-blast residue in order to estimate the presence of interferers. This would reduce the risk of false positives. Additionally, when interferers are detected, washing can be employed for more reliable routine analysis. We suggest at least 3 wash cycles. This method could be used for ordinary commercial materials, which are cheap and easily obtained.

Identification of Luminescent Markers for Gunshot Residues: Fluorescence, Raman Spectroscopy, and Chemometrics.

Gunshot residue (GSR) is an evidence of major importance in firearm-related crimes. The recent introduction of nontoxic ammunition has made impossible the characterization of GSR particles by the current methods employed by forensic experts. To overcome this drawback, the introduction of luminescent markers was proposed, allowing on-site visual detection of luminescent gunshot residue (LGSR) at the crime scene. Three different luminescent markers coordinated with europium for specific and selective encoding of ammunition have been proposed. To promote a variety of versatile tools for GSR analysis, spectroscopic techniques combined with chemometric methods can be applied to achieve a reliable, fast, and nondestructive means to identify LGSR and discriminate among the different markers. Luminescence (emission and excitation), normal, and resonance Raman spectroscopies associated with principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were evaluated. The classification model using the complementary information on emission and excitation spectra, a.k.a. data fusion, provided a 100% correct classification for all markers. A comprehensive study has been developed to show that the insertion of luminescent markers enables not only the easy localization of GSR residues but also the possibility of ammunition encoding through the use of multivariate classification methods.

Investigation of the use of luminescent markers as gunshot residue indicators.

The addition of luminescent markers into ammunition cartridges is an appealing proposal to achieve a greater individual identification of the ammunition. The lanthanide elements present in these luminescent materials act as characteristic chemical markers that, also, offer the great benefit of making gunshot residues (GSR) collection easier. Although the use of luminescent markers offers numerous advantages, and can be a reliable future option in the cartridge ammunition market, little or nothing is known about the interaction of the marker with the ammunition compounds after the shot. For the forensic laboratories, it is of utmost importance to anticipate the commercialization of tagged luminescent ammunition by knowing the type of particles produced after the discharge. That is, to investigate if markers merge with GSR to form single particles or, on the contrary, they form individual particles that travel separately from the GSR particles. In this work, conventional ammunition cartridges tagged with two types of luminescent markers were shot. Then, the particles produced were visualized under UV light on the floor, clothing targets and the shooter. The luminescent particles spread over the floor determined the shooter position and the bullet trajectory. The illumination of the shot targets allows the visualization of the GSR patterns only using a portable UV lamp, avoiding the use of colorimetric test. The GSR particles were collected and subjected to SEM-EDX and Raman spectroscopy analysis to get information about their inorganic and organic composition. The results indicated that part of the marker and the GSR merge and travel together. With this, particles composed by the marker and propellant organic compounds can be identified by Raman spectroscopy, and the unequivocal identification of the GSR and the marker can be achieved by SEM-EDX. Consequently, the luminescent particles detected under UV light improve the evidence collection and offer information about the GSR and the marker. Additionally, this study support the use of luminescent ammunition to study, for example, the transfer or persistence of GSR.

Application of the Metal-Organic Framework [Eu(BTC)] as a Luminescent Marker for Gunshot Residues: A Synthesis, Characterization, and Toxicity Study.

The 3D metal-organic framework (MOF) [Eu(BTC)] (where BTC = trimesic acid) was synthesized in 20 min by a microwave-assisted hydrothermal method with a yield of 89%. A structural and spectroscopic study, performed by X-ray diffraction, thermogravimetry, and photoluminescence spectroscopy, showed that this framework has high crystallinity, thermal stability, and luminescence. This MOF had a red-orange luminescence when excited with ultraviolet (UV) radiation (λ = 254 nm) and a high potential for use as a luminescent marker for gunshot residues (GSR). When added to 9 mm nontoxic ammunition, it greatly improved quality of the crime scene investigation, allowing for direct visualization of the luminescent GSR on the shooter's hand and firearm and at the firing range using only a portable UV lamp. The marked luminescent GSR was easily collected and characterized by nondestructive techniques, including with a Video Spectral Comparator and scanning electron microscopy/energy-dispersive spectroscopy, wherein the presence of Eu3+ ions was confirmed. Furthermore, the oral acute toxicity of this MOF was assessed in adult female Wistar rats using the Organisation for Economic Cooperation and Development 423 guidelines. This study classified the MOF [Eu(BTC)] in a less toxic Globally Harmonized System category (category 5), with a LD50 (lethal dose) of 5000 mg/kg, ensuring a wide security range for its application.

Annealing effects on the photocatalytic activity of ZnO nanoparticles.

This paper describes the development of ZnO nanoparticles by a chemical method, to test them in the photocatalysis of the degradation of textile dyes, using Rhodamine B (RhB) as a probe reaction. The samples were submitted to different heat treatments in order to observe the annealing effects on the photocatalytical properties, surface decontamination and the consequent particle change, in terms of crystallinity. The as-prepared samples (ZOA) correspond to a metastable phase (oxy or hydroxy zinc acetate) and post annealing leads to ZnO crystallization. In spite of the XRD patterns showing only the ZnO phase for heat treatment at 100 degrees C, FTIR data show that carboxylate groups remains attached to the ZnO surface up to 300 degrees C. Up to 300 degrees C the presence of these carboxylate groups, provided by the synthesis method, showed to be more relevant to photoactivity than the specific surface area. At higher temperatures, crystallinity becomes the dominant factor and an increasing of crystallinity favors the photoactivity.