Progress toward the determination of correct classification rates in fire debris analysis.

Principal components analysis (PCA), linear discriminant analysis (LDA), and quadratic discriminant analysis (QDA) were used to develop a multistep classification procedure for determining the presence of ignitable liquid residue in fire debris and assigning any ignitable liquid residue present into the classes defined under the American Society for Testing and Materials (ASTM) E 1618-10 standard method. A multistep classification procedure was tested by cross-validation based on model data sets comprised of the time-averaged mass spectra (also referred to as total ion spectra) of commercial ignitable liquids and pyrolysis products from common building materials and household furnishings (referred to simply as substrates). Fire debris samples from laboratory-scale and field test burns were also used to test the model. The optimal model's true-positive rate was 81.3% for cross-validation samples and 70.9% for fire debris samples. The false-positive rate was 9.9% for cross-validation samples and 8.9% for fire debris samples.

Discriminant analysis in the presence of interferences: combined application of target factor analysis and a Bayesian soft-classifier.

A method is described for performing discriminant analysis in the presence of interfering background signal. The method is based on performing target factor analysis on a data set comprised of contributions from analyte(s) and interfering components. A library of data from representative analyte classes is tested for possible contributing factors by performing oblique rotations of the principal factors to obtain the best match, in a least-squares sense, between test and predicted vectors. The degree of match between the test and predicted vectors is measured by the Pearson correlation coefficient, r, and the distribution of r for each class is determined. A Bayesian soft classifier is used to calculate the posterior probability based on the distributions of r for each class, which assist the analyst in assessing the presence of one or more analytes. The method is demonstrated by analyses performed on spectra obtained by laser induced breakdown spectroscopy (LIBS). Single and multiple bullet jacketing transfers to steel and porcelain substrates were analyzed to identify the jacketing materials. Additionally, the metal surrounding bullet holes was analyzed to identify the class of bullet jacketing that passed through a stainless steel plate. Of 36 single sample transfers, the copper jacketed (CJ) and non-jacketed (NJ) class on porcelain had an average posterior probability of the metal deposited on the substrate of 1.0. Metal jacketed (MJ) bullet transfers to steel and porcelain were not detected as successfully. Multiple transfers of CJ/NJ and CJ/MJ on the two substrates resulted in posterior probabilities that reflected the presence of both jacketing materials. The MJ/NJ transfers gave posterior probabilities that reflected the presence of the NJ material, but the MJ component was mistaken for CJ on steel, while non-zero probabilities were obtained for both CJ and MJ on porcelain. Jacketing transfer from a bullet to steel as the projectile passed through the steel also proved difficult to analyze. Over 50% of the samples left insufficient transfer to be identified. Transfer from NJ and CJ jacketing was successfully identified by posterior probabilities greater than 0.8.

Analysis of black writing ink by electrospray ionization mass spectrometry.

A method for the analysis of dyes and vehicles within writing inks was developed. The method was tested on a set of 18 black ink pens comprised of 6 ballpoint, 6 gel, and 6 rollerball pens. The sampling procedure utilized a small number of ink-coated paper fibers collected surreptitiously from the document, causing minimal damage and providing a sufficient quantity of ink for analysis. Methanol proved suitable for the extraction of ink components from ballpoint, gel and rollerball pens. Three separate electrospray ionisation-mass spectrometry (ESI-MS) methods were required to detect the dyes and vehicles from the inks. The ions present in the ESI-MS spectra at a signal-to-noise ratio of greater than 3:1 provided sufficient information to allow differentiation between the inks of each type. A tentative identification of the ink components was made based on a comparison of the ions present in the ink extract ESI-MS spectra with the ions present in a series of standards. The limits of detection for the standards were generally in the 2.5-10 ppm range. The method reported here extends the ESI-MS method of ink analysis to include gel and rollerball pens, includes the analysis of vehicles as well as dyes in the inks and demonstrates a minimally destructive sampling method that does not require a "biopsy" of the document.