RESUMO
Seventeen laboratories participated in three interlaboratory exercises to assess the performance of refractive index, micro X-ray Fluorescence Spectroscopy (µXRF), and Laser Induced Breakdown Spectroscopy (LIBS) data for the forensic comparison of glass samples. Glass fragments from automotive windshields were distributed to the participating labs as blind samples and participants were asked to compare the glass samples (known vs. questioned) and report their findings as they would in casework. For samples that originated from the same source, the overall correct association rate was greater than 92% for each of the three techniques (refractive index, µXRF, and LIBS). For samples that originated from different vehicles, an overall correct exclusion rate of 82%, 96%, and 87% was observed for refractive index, µXRF, and LIBS, respectively. Special attention was given to the reporting language used by practitioners as well as the use of verbal scales and/or databases to assign a significance to the evidence. Wide variations in the reported conclusions exist between different laboratories, demonstrating a need for the standardization of the reporting language used by practitioners. Moreover, few labs used a verbal scale and/or a database to provide a weight to the evidence. It is recommended that forensic practitioners strive to incorporate the use of a verbal scale and/or a background database, if available, to provide a measure of significance to glass forensic evidence (i.e., the strength of an association or exclusion).
RESUMO
Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) has been shown to be an excellent technique for the discrimination of glass originating from different sources and for the association of glass originating from the same source. Typically, a match criterion is used to compare the elemental profile of the known sample to a questioned sample and if the glass samples are determined to "match" this may be followed by the use of a verbal scale to report the forensic practitioner's conclusion. This approach has several disadvantages: a fixed match criterion suffers from the "fall-off-the-cliff effect," the rarity of an elemental profile is not taken into account, and the use of a verbal scale to assign a weight of evidence may be considered as subjective and can vary by examiner. An alternative approach includes the use of a continuous likelihood ratio that provides a quantitative measure of the value of the evidence in support of any hypothesis and accounts for the rarity of an elemental profile through the use of a glass database. In the present study, two glass databases were used to evaluate the performance of the likelihood ratio; the first database includes 420 automotive windshield samples, while the second database includes 385 glass samples from casework. The multivariate kernel model was used for the calculation of the likelihood ratio. However, this model led to unreasonably large (or small) likelihood ratios. Thus, a calibration step, using the Pool Adjacent Violators (PAV) algorithm, was necessary in order to limit the likelihood ratio to reasonable values. The calibrated likelihood ratio presented rates of misleading evidence of <1.5% (for LRs<1 when objects came from the same source), and of <1.0% (for LRs>1 when objects came from different sources), which improved over the analogous ASTM false inclusion and false exclusion rates previously reported. In addition, the likelihood ratio limited the magnitude of the misleading evidence, providing only weak to moderate support for the incorrect hypothesis. Finally, most of the pairs found to present LR>1 when objects originated from different sources were explained by similarity of manufacturer of the glass source.
RESUMO
Milk has been reported as one of the most adulterated foodstuffs in the developed and developing world. One way to detect adulteration is to determine whether the country of origin on the label could be the actual country of origin. Such profiling may be accomplished through the use of elemental analysis techniques, however this is a preliminary study and this goal is not yet met. In this study, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method was developed for the analysis of solid milk powder and compared to k0-instrumental neutron activation analysis (k0-INAA) for a reference milk material (IAEA-153) as well as several milk samples from different countries. The analytical figures of merit for both the LA-ICP-MS and the k0-INAA analysis are reported. Precision of ~ 10% RSD or better was achieved for most elements for both techniques and bias of ~ 10% was achieved for both techniques for most elements with LA-ICP-MS producing lower limits of detection (~ 1â¯mg/kg) for Sr. The comparison of LA-ICP-MS to k0-INAA showed overlap of the 95% confidence intervals for all comparison samples. A total of 68 authentic milk powder samples representing 5 different countries (Argentina, Russia, Singapore, Slovenia, and the United States) were analyzed to determine whether multivariate elemental differences between the countries were sufficiently larger than within country differences in order to visualize groupings by country. Principle component analysis (PCA) using Na, Mg, Ca, Rb, and Sr show different groups for the United States, Argentina, Singapore, and Slovenia samples of limited representation for each country. However the large number and geographic distribution of samples from Russia were not able to be distinguished from the samples from the United States and Slovenia.