Browsing by Subject "multivariate statistics"

Now showing 1 - 4 of 4
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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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    Combining Multivariate Statistical Methods and Spatial Analysis to Characterize Water Quality Conditions in the White River Basin, Indiana, U.S.A.
    (2011-02-25) Gamble, Andrew Stephan; Babbar-Sebens, Meghna; Tedesco, Lenore P.; Peng, Hanxiang
    This research performs a comparative study of techniques for combining spatial data and multivariate statistical methods for characterizing water quality conditions in a river basin. The study has been performed on the White River basin in central Indiana, and uses sixteen physical and chemical water quality parameters collected from 44 different monitoring sites, along with various spatial data related to land use – land cover, soil characteristics, terrain characteristics, eco-regions, etc. Various parameters related to the spatial data were analyzed using ArcHydro tools and were included in the multivariate analysis methods for the purpose of creating classification equations that relate spatial and spatio-temporal attributes of the watershed to water quality data at monitoring stations. The study compares the use of various statistical estimates (mean, geometric mean, trimmed mean, and median) of monitored water quality variables to represent annual and seasonal water quality conditions. The relationship between these estimates and the spatial data is then modeled via linear and non-linear multivariate methods. The linear statistical multivariate method uses a combination of principal component analysis, cluster analysis, and discriminant analysis, whereas the non-linear multivariate method uses a combination of Kohonen Self-Organizing Maps, Cluster Analysis, and Support Vector Machines. The final models were tested with recent and independent data collected from stations in the Eagle Creek watershed, within the White River basin. In 6 out of 20 models the Support Vector Machine more accurately classified the Eagle Creek stations, and in 2 out of 20 models the Linear Discriminant Analysis model achieved better results. Neither the linear or non-linear models had an apparent advantage for the remaining 12 models. This research provides an insight into the variability and uncertainty in the interpretation of the various statistical estimates and statistical models, when water quality monitoring data is combined with spatial data for characterizing general spatial and spatio-temporal trends.
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    Multivariate Statistical Methods Applied to the Analysis of Trace Evidence
    (2013-08-22) Szkudlarek, Cheryl Ann; Goodpaster, John V. (John Vincent); Picard, Christine; Siegel, Jay A.; Minto, Robert
    The aim of this study was to use multivariate statistical techniques to: (1) determine the reproducibility of fiber evidence analyzed by MSP, (2) determine whether XRF is an appropriate technique for forensic tape analysis, and (3) determine if DART/MS is an appropriate technique for forensic tape analysis. This was achieved by employing several multivariate statistical techniques including agglomerative hierarchical clustering, principal component analysis, discriminant analysis, and analysis of variance. First, twelve dyed textile fibers were analyzed by UV-Visible MSP. This analysis included an inter-laboratory study, external validations, differing preprocessing techniques, and color coordinates. The inter-laboratory study showed no statistically significant difference between the different instruments. The external validations had overall acceptable results. Using first derivatives as a preprocessing technique and color coordinates to define color did not result in any additional information. Next, the tape backings of thirty-three brands were analyzed by XRF. After chemometric analysis it was concluded that the 3M tapes with black adhesive can be classified by brand except for Super 33+ (Cold Weather) and Super 88. The colorless adhesive tapes were separated into two large groups which were correlated with the presence of aluminosilicate filler. Overall, no additional discrimination was seen by using XRF compared to the traditional instrumentation for tape analysis previously published. Lastly, the backings of eighty-nine brands of tape were analyzed by DART/MS. The analysis of the black adhesive tapes showed that again discrimination between brands is possible except for Super 33+ and Super 88. However, now Tartan and Temflex have become indistinguishable. The colorless adhesive tapes again were more or less indistinguishable from one another with the exception of Tuff Hand Tool, Qualpack, and a roll of 3M Tartan, which were found to be unique. It cannot be determined if additional discrimination was achieved with DART/MS because the multivariate statistical techniques have not been applied to the other instrumental techniques used during tape analysis.