Browsing by Subject "chemometrics"

Now showing 1 - 5 of 5
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    Advances in Solid Phase Microextraction for the Analysis of Volatile Compounds in Explosives, Tire Treatments, and Entomological Specimens
    (2016-05) Kranz, William D.; Goodpaster, John V.; Manicke, Nick; Sardar, Rajesh; Picard, Christine Johanna; Long, Eric C.
    Solid phase micro-extraction is a powerful and versatile technique, well-suited to the analysis of numerous samples of forensic interest. The exceptional sensitivity of the SPME platform, combined with its adaptability to traditional GC-MS systems and its ability to extract samples with minimal work-up, make it appropriate to applications in forensic laboratories. In a series of research projects, solid phase micro-extraction was employed for the analysis of explosives, commercial tire treatments, and entomological specimens. In the first project, the volatile organic compounds emanating from two brands of pseudo-explosive training aids for use in detector dog imprinting were determined by SPME-GC-MS, and the efficacy of these training materials was tested in live canine trials. In the second project, the headspace above various plasticizers was analyzed comparative to that of Composition C-4 in order to draw conclusions about the odor compound, 2- ethyl-1-hexnaol, with an eye toward the design of future training aids. In the third, automobile tires which had participated in professional race events were analyzed for the presence of illicit tire treatments, and in the fourth, a novel SPME-GC-MS method was developed for the analysis of blowfly (Diptera) liquid extracts. In the fifth and final project, the new method was put to the task of performing a chemotaxonomic analysis on pupa specimens, seeking to chemically characterize them according to their age, generation, and species.
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    Chemometrics applied to the discrimination of synthetic fibers by microspectrophotometry
    (2014-01-03) Reichard, Eric Jonathan; Goodpaster, John V. (John Vincent); Minto, Robert; Sardar, Rajesh; Siegel, Jay A.; Picard, Christine
    Microspectrophotometry is a quick, accurate, and reproducible method to compare colored fibers for forensic purposes. The use of chemometric techniques applied to spectroscopic data can provide valuable discriminatory information especially when looking at a complex dataset. Differentiating a group of samples by employing chemometric analysis increases the evidential value of fiber comparisons by decreasing the probability of false association. The aims of this research were to (1) evaluate the chemometric procedure on a data set consisting of blue acrylic fibers and (2) accurately discriminate between yellow polyester fibers with the same dye composition but different dye loadings along with introducing a multivariate calibration approach to determine the dye concentration of fibers. In the first study, background subtracted and normalized visible spectra from eleven blue acrylic exemplars dyed with varying compositions of dyes were discriminated from one another using agglomerative hierarchical clustering (AHC), principal component analysis (PCA), and discriminant analysis (DA). AHC and PCA results agreed showing similar spectra clustering close to one another. DA analysis indicated a total classification accuracy of approximately 93% with only two of the eleven exemplars confused with one another. This was expected because two exemplars consisted of the same dye compositions. An external validation of the data set was performed and showed consistent results, which validated the model produced from the training set. In the second study, background subtracted and normalized visible spectra from ten yellow polyester exemplars dyed with different concentrations of the same dye ranging from 0.1-3.5% (w/w), were analyzed by the same techniques. Three classes of fibers with a classification accuracy of approximately 96% were found representing low, medium, and high dye loadings. Exemplars with similar dye loadings were able to be readily discriminated in some cases based on a classification accuracy of 90% or higher and a receiver operating characteristic area under the curve score of 0.9 or greater. Calibration curves based upon a proximity matrix of dye loadings between 0.1-0.75% (w/w) were developed that provided better accuracy and precision to that of a traditional approach.
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    Instrumental and Chemometric Analysis of Automotive Clear Coat Paints by Micro Laser Raman and UV Microspectrophotometry
    (2012-07-19) Mendlein, Alexandra Nicole; Siegel, Jay A.; Goodpaster, John V. (John Vincent); Li, Lei
    Automotive paints have used an ultraviolet (UV) absorbing clear coat system for nearly thirty years. These clear coats have become of forensic interest when comparing paint transfers and paint samples from suspect vehicles. Clear coat samples and their ultraviolet absorbers are not typically examined or characterized using Raman spectroscopy or microspectrophotometry (MSP), however some past research has been done using MSP. Chemometric methods are also not typically used for this characterization. In this study, Raman and MSP spectra were collected from the clear coats of 245 American and Australian automobiles. Chemometric analysis was subsequently performed on the measurements. Sample preparation was simple and involved peeling the clear coat layer and placing the peel on a foil-covered microscope slide for Raman or a quartz slide with no cover slip for MSP. Agglomerative hierarchical clustering suggested three classes of spectra, and principal component analysis confirmed this. Factor loadings for the Raman data illustrated that much of the variance between spectra came from specific regions (400 – 465 cm-1, 600 – 660 cm-1, 820 – 885 cm-1, 950 – 1050 cm-1, 1740 – 1780 cm-1, and 1865 – 1900 cm-1). For MSP, the regions of highest variance were between 230 – 270 nm and 290 – 370 nm. Discriminant analysis showed that the three classes were well-differentiated with a cross-validation accuracy of 92.92% for Raman and 91.98% for MSP. Analysis of variance attributed differentiability of the classes to the regions between 400 – 430 cm-1, 615 – 640 cm-1, 825 – 880 cm-1, 1760 – 1780 cm-1, and 1860 – 1900 cm-1 for Raman spectroscopy. For MSP, these regions were between 240 – 285 nm and 300 – 370 nm. External validation results were poor due to excessively noisy spectra, with a prediction accuracy of 51.72% for Raman and 50.00% for MSP. No correlation was found between the make, model, and year of the vehicles using either method of analysis.
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    Instrumental and Statistical Methods for the Comparison of Class Evidence
    (2011-03-09) Liszewski, Elisa Anne; Goodpaster, John V. (John Vincent); Siegel, Jay A.; Deo, Sapna K.
    Trace evidence is a major field within forensic science. Association of trace evidence samples can be problematic due to sample heterogeneity and a lack of quantitative criteria for comparing spectra or chromatograms. The aim of this study is to evaluate different types of instrumentation for their ability to discriminate among samples of various types of trace evidence. Chemometric analysis, including techniques such as Agglomerative Hierarchical Clustering, Principal Components Analysis, and Discriminant Analysis, was employed to evaluate instrumental data. First, automotive clear coats were analyzed by using microspectrophotometry to collect UV absorption data. In total, 71 samples were analyzed with classification accuracy of 91.61%. An external validation was performed, resulting in a prediction accuracy of 81.11%. Next, fiber dyes were analyzed using UV-Visible microspectrophotometry. While several physical characteristics of cotton fiber can be identified and compared, fiber color is considered to be an excellent source of variation, and thus was examined in this study. Twelve dyes were employed, some being visually indistinguishable. Several different analyses and comparisons were done, including an inter-laboratory comparison and external validations. Lastly, common plastic samples and other polymers were analyzed using pyrolysis-gas chromatography/mass spectrometry, and their pyrolysis products were then analyzed using multivariate statistics. The classification accuracy varied dependent upon the number of classes chosen, but the plastics were grouped based on composition. The polymers were used as an external validation and misclassifications occurred with chlorinated samples all being placed into the category containing PVC.
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    Monitoring, characterizing, and preventing microbial degradation of ignitable liquids on soil
    (2013) Turner, Dee Ann; Goodpaster, John V. (John Vincent); Michalski, Greg M.; Blacklock, Brenda J.; Siegel, Jay A.; Long, Eric C. (Eric Charles)
    Organic-rich substrates such as soil provide an excellent carbon source for bacteria. However, hydrocarbons such as those found in various ignitable liquids can also serve as a source of carbon to support bacterial growth. This is problematic for fire debris analysis as samples may be stored at room temperature for extended periods before they are analyzed due to case backlog. As a result, selective loss of key components due to bacterial metabolism can make identifying and classifying ignitable liquid residues by their chemical composition and boiling point range very difficult. The ultimate goal of this project is to preserve ignitable liquid residues against microbial degradation as efficiently and quickly as possible. Field and laboratory studies were conducted to monitor microbial degradation of gasoline and other ignitable liquids in soil samples. In addition to monitoring degradation in potting soil, as a worst case scenario, the effect of soil type and season were also studied. The effect of microbial action was also compared to the effect of weathering by evaporation (under nitrogen in the laboratory and by the passive headspace analysis of the glass fragments from the incendiary devices in the field studies). All studies showed that microbial degradation resulted in the significant loss of n-alkanes and lesser substituted alkylbenzenes predominantly and quickly, while more highly substituted alkanes and aromatics were not significantly affected. Additionally, the residential soil during the fall season showed the most significant loss of these compounds over the course of 30 days. To combat this problem, a chemical solution is to be immediately applied to the samples as they are collected. Various household and commercial products were tested for their efficacy at low concentrations to eliminate all living bacteria in the soil. Triclosan (2% (w/v) in NaOH) proved to be the most effective at preserving ignitable liquid residues for at least 30 days.