Candice Bridge

Characterization of Automobile Float Glass with Laser-Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Mass Spectrometry

A comparative analysis of the discriminating power of laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), each coupled with refractive index (RI) measurements, is presented for a study of 23 samples of automobile float glass. Elemental emission intensity ratios (LIBS) and elemental concentration ratios (LA-ICP-MS) and their associated confidence intervals were calculated for each float glass sample. The ratios and confidence intervals were used to determine the discrimination power of each analytical method. It was possible to discriminate 83% of the glass samples with 99% confidence based on LIBS spectra alone, and 96–99% of the samples could be discriminated based on LIBS spectra taken in conjunction with RI data at the same confidence level. LA-ICP-MS data allowed for 100% discrimination of the samples without the need for RI data. The results provide evidence to support the use of LIBS combined with RI for forensic analysis of float glass in laboratories that do not have access to LA-ICP-MS.

Atmosphere issues in detection of explosives and organic residues

This study makes a comparison of LIBS emission from molecular species in plasmas produced from organic residues on a non-metallic substrate by both a 5 ns Nd:YAG laser (1064 nm) and a 40 fs Ti:Sapphire laser (800 nm) in air and argon atmospheres. The organic samples analyzed had varying amounts of carbon, nitrogen, hydrogen, and oxygen in their molecular structure. The characterization was based on the atomic carbon, hydrogen, nitrogen, and oxygen lines as well as the diatomic species CN (B2Σ+ - X2Σ+) and the C2 (d3Πg - a3Πu). Principal Component Analysis (PCA) was used to identify similarities of the organic analyte via the emission spectra. The corresponding Receiver Operating Characteristics (ROC) curves show the limitations of the PCA model for the nanosecond regime in air.

Molecular signal as a signature for detection of energetic materials in filament-induced breakdown spectroscopy

Laser Induced Breakdown Spectroscopy (LIBS) by self-channeled femtosecond pulses is characterized for detection of energetic materials. Different polymers are spin coated on silicon wafers to provide a thin organic layer with controllable thickness ranging from 500 nm to 1 μm. Spectral analysis of atomic and molecular carbon emission shows CN molecular signal from samples that do not contain nitrogen. This can be explained by possible molecular recombination between native atomic carbon and atmospheric nitrogen. As a consequence, caution must be exercised when using spectral signatures based on CN emission for explosive detection by filament-induced LIBS.

Adsorption Saturation and Chromatographic Distortion Effects on Passive Headspace Sampling with Activated Charcoal in Fire Debris Analysis

Distortion of the chromatographic profile obtained for hydrocarbons that have been sampled by adsorption onto activated charcoal is a well-known phenomenon. The work reported here helps to better define the causes of chromatographic profile distortion and offers a potential method to avoid chromatographic distortion in some cases through a subsampling technique. The recovery of hydrocarbons from an equimolar mixture was investigated to determine the influence of hydrocarbon concentration on the molar ratios of recovered components. In a one-quart container, hydrocarbon volumes as small as 24 microL (liquid) were sufficient to saturate the surface area available for adsorption on a 99.0 mm2 square of activated charcoal, resulting in significant distortions in the molar ratio and the chromatographic profile of the recovered hydrocarbons. Passive headspace sampling of a similarly small volume of unweathered gasoline spiked onto carpet padding resulted in a significant distortion of the chromatographic profile. The chromatographic profile of the recovered hydrocarbons closely resembled 75% weathered gasoline. Heating the container spiked with unweathered gasoline to evenly distribute the components and then removing a subsample of the carpet padding to a second container for passive headspace analysis greatly reduced the amount of distortion in the resulting chromatogram.

Characterizing and classifying water-based lubricants using direct analysis in real time®time of flight mass spectrometry

Lubricant analysis is a relatively recent addition to the examination protocol in sexual assault cases by the forensic science community. Currently, lubricants cannot be unequivocally identified, although their presence can be determined based on the detection of a few chemical components, i.e. polydimethylsiloxane, polyethylene glycol, glycerol or nonoxynol-9. Confirmation of their presence typically requires that an authentic reference sample be submitted and compared to the unknown sample to determine if they potentially came from the same source. In this study, 33 individual personal water-based lubricants were characterized by direct analysis in real time-time of flight mass spectroscopy (DART-TOFMS). The resultant mass spectral data were evaluated using well-established multivariate statistical techniques, such as principal component and linear discriminant analysis. Statistical analysis revealed six different groupings within the data that could be correlated to sub-categories of water-based lubricants that contain additives in the form of anesthetics, sensation enhancers and flavorings. This variability in the personal lubricant sources can be utilized to aid in identifying the specific type of lubricant when only a questioned sample is available.

Quantifying the degradation of TNT and RDX in a saline environment with and without UV-exposure

Terrorist attacks in a maritime setting, such as the bombing of the USS Cole in 2000, or the detection of underwater mines, require the development of proper protocols to collect and analyse explosive material from a marine environment. In addition to proper analysis of the explosive material, protocols must also consider the exposure of the material to potentially deleterious elements, such as UV light and salinity, time spent in the environment, and time between storage and analysis. To understand how traditional explosives would be affected by such conditions, saline solutions of explosives were exposed to natural and artificial sunlight. Degradation of the explosives over time was then quantified using negative chemical ionization gas chromatography mass spectrometry (GC/NCI-MS). Two explosives, trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX), were exposed to different aqueous environments and light exposures with salinities ranging from freshwater to twice the salinity of ocean water. Solutions were then aged for up to 6 months to simulate different conditions the explosives may be recovered from. Salinity was found to have a negligible impact on the degradation of both RDX and TNT. RDX was stable in solutions of all salinities while TNT solutions degraded regardless of salinity. Solutions of varying salinities were also exposed to UV light, where accelerated degradation was seen for both explosives. Potential degradation products of TNT were identified using electrospray ionization mass spectrometry (ESI-MS), and correspond to proposed degradation products discussed in previously published works [1].

Chemical discrimination of lubricant marketing types using direct analysis in real time time‐of‐flight mass spectrometry

RATIONALE In comparison to other violent crimes, sexual assaults suffer from very low prosecution and conviction rates especially in the absence of DNA evidence. As a result, the forensic community needs to utilize other forms of trace contact evidence, like lubricant evidence, in order to provide a link between the victim and the assailant. METHODS In this study, 90 personal bottled and condom lubricants from the three main marketing types, silicone-based, water-based and condoms, were characterized by direct analysis in real time time of flight mass spectrometry (DART-TOFMS). The instrumental data was analyzed by multivariate statistics including hierarchal cluster analysis, principal component analysis, and linear discriminant analysis. RESULTS By interpreting the mass spectral data with multivariate statistics, 12 discrete groupings were identified, indicating inherent chemical diversity not only between but within the three main marketing groups. A number of unique chemical markers, both major and minor, were identified, other than the three main chemical components (i.e. PEG, PDMS and nonoxynol-9) currently used for lubricant classification. The data was validated by a stratified 20% withheld cross-validation which demonstrated that there was minimal overlap between the groupings. CONCLUSIONS Based on the groupings identified and unique features of each group, a highly discriminating statistical model was then developed that aims to provide the foundation for the development of a forensic lubricant database that may eventually be applied to casework. Copyright

Determining the effect of cartridge case coatings on GSR using post-fire priming cup residue

Ammunition is typically composed of a lead-based priming mixture which contributes to the characteristics most commonly used for the identification of gunshot residue (GSR). Due to the health risks often associated with lead, the use of lead-free primers in ammunitions is becoming more popular. Thus, the presence of GSR is becoming more difficult to discern based on the traditional means, i.e. the presence of lead (Pb), barium (Ba), and antimony (Sb). While research has been conducted on the differences between lead-based and lead-free muzzle discharge residue, few have researched other components of ammunition which may lead to other means of characterizing GSR. This research, therefore, covers that gap by focusing on the priming cup present in ammunition and the residue which may originate from it, that can contribute to muzzle discharge residue. In this study, a lead-based and a lead-free ammunition from four different manufacturers were chosen. The cartridges were fired using a Glock 17, 9mm Parabellum, collected post-fire, and subsequently de-primed resulting in the removal of the anvil. The GSR present on the anvils and cups was analyzed using scanning electron microscopy coupled with energy dispersive x-ray spectrometry (SEM-EDX). The data was then processed using unit vector analysis for normalization and analyzed using principal component analysis (PCA) and linear discriminant analysis (LDA). This data was then used to determine the components of the cartridge case which contribute to GSR and develop a method of characterization between lead-free and lead-based ammunition. Such a method will improve the detection of GSR by strengthening the criteria of identification.

Analysis and classification of smokeless powders by GC–MS and DART-TOFMS

Partially burned smokeless powder particles may be present as a form of evidence following a shooting or explosive event, such as the explosion of a pipe bomb. The characterization and classification of residual smokeless powers may allow for a known sample, i.e. sample collected from a suspect, to be connected to an unknown sample, i.e. sample obtained from a crime scene. In this study, thirty-four (34) smokeless powders were analyzed using GC-MS and DART-TOFMS to determine how comparable the discriminatory power of each instrument was based on the smokeless powder constituents identified within each sample. Analysis of smokeless powders by DART-TOFMS generated comparable results to GC-MS in a fraction of the time (∼30seconds). Most peaks observed between the instruments were the same; however, N-nitroso-DPA was only observed in the DART-TOFMS spectra but was not a significant contributor. Samples were naturally grouped together using hierarchical cluster analysis and principal component analysis, based on underlying features in the resulting spectra. Samples were placed into groupings based on significant peaks observed and relative intensities. Classification models were presented for both GC-MS and DART-TOFMS and subsequently tested and compared. The classification models used in this study were linear discriminant analysis, k-nearest neighbors, and random forest modeling. The groups observed were similar between the two instruments, indicating that DART-TOFMS provides comparable data to GC-MS and could be used as a rapid screening technique.

DART-MS: A New Analytical Technique for Forensic Paint Analysis

Automotive paint evidence is one of the most significant forms of evidence obtained in automotive-related incidents. Therefore, the analysis of automotive paint evidence is imperative in forensic casework. Most analytical schemes for automotive paint characterization involve optical microscopy, followed by infrared spectroscopy and pyrolysis-gas chromatography mass spectrometry ( py-GCMS) if required. The main drawback with py-GCMS, aside from its destructive nature, is that this technique is relatively time intensive in comparison to other techniques. Direct analysis in real-time-time-of-flight mass spectrometry (DART-TOFMS) may provide an alternative to py-GCMS, as the rapidity of analysis and minimal sample preparation affords a significant advantage. In this study, automotive clear coats from four vehicles were characterized by DART-TOFMS and a standard py-GCMS protocol. Principal component analysis was utilized to interpret the resultant data and suggested the two techniques provided analogous sample discrimination. Moreover, in some instances DART-TOFMS was able to identify components not observed by py-GCMS and vice versa, which indicates that the two techniques may provide complementary information. Additionally, a thermal desorption/pyrolysis DART-TOFMS methodology was also evaluated to characterize the intact paint chips from the vehicles to ascertain if the linear temperature gradient provided additional discriminatory information. All the paint samples were able to be discriminated based on the distinctive thermal desorption plots afforded from this technique, which may also be utilized for sample discrimination. On the basis of the results, DART-TOFMS may provide an additional tool to the forensic paint examiner.