This dissertation will focus on the extraction of volatile organic compounds associated with gunshot residue from articles of clothing, followed by analysis with mass spectrometry. During the discharge of a weapon, a cloud of volatile organic gunshot residue (OGSR) is dispersed around a firearm. This will create a high probability of transfer between the OGSR and the clothing of individuals who are near a discharged weapon. The first part of this dissertation will be the development of a method for removal of volatile OGSR from articles of clothing. Extraction of OGSR will be completed by solid phase microextraction (SPME), followed by separation and analysis by gas chromatography-mass spectrometry (GC/MS). Many parameters will require optimization for proper extraction of OGSR from articles of clothing. Following development of a SPME procedure, figures of merit were determined such as linearity and limits of detection/quantification, obtaining levels of detection of 0.206 ng/cm2 on a 100 cm2 cotton cloth. Applications of this extraction method were investigated including the determination of the distance OGSR travels from a discharged weapon and the extraction of OGSR with different clothing materials by SPME. The second part of this dissertation will focus on the development of an on-line solvent extraction method for removal of OGSR from articles of clothing, followed by analysis with paper spray mass spectrometry. Issues using SPME of certain types of clothing materials required the development of an alternative method for removal of OGSR from articles of clothing. Use of an on-line solvent extraction technique of OGSR from articles of clothing followed by analysis with paper spray mass spectrometry allowed for detection of OGSR at comparable levels to a headspace SPME procedure. Use of paper spray with an ion trap mass spectrometer permitted the soft ionization of OGSR compounds followed by tandem mass spectrometry to obtain structural information. Extraction of OGSR from articles of clothing has potential to determine if an individual was present during the discharge of a firearm. Extraction of OGSR from articles of clothing will provide an alternative to traditional methods of gunshot residue analysis currently in use.

Gunshot residue (GSR) analysis is a crucial aspect of the investigation of firearms-related incidents. The presence of GSR on a person or surface can provide valuable insight regarding proximity or involvement of an individual in a shooting incident. Traditionally, GSR analysis relies on the detection of inorganic compounds within the ammunition, known as inorganic gunshot residue (IGSR). These inorganic compounds are comprised of lead, barium, and antimony. IGSR compounds originate from the content of the primer, and each individual element is expelled during discharge, fused while molten, and land on nearby surfaces. Stubs with an adhesive coat are used to collect these particles by pressing against a surface suspected to have GSR particles. The current analytical method for detection and identification of IGSR, Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy (SEM/EDS), surveys GSR stubs for both the elemental composition as well as the morphology of the compounds. Positive identification requires both the elemental composition and spherical morphology of IGSR. Several issues exist with the nature of IGSR as well as the current method of analysis. Identification by SEM/EDS not only requires time for transportation and labor but may also produce false negatives due to inconsistent shape or lack of all three elements. The development of a rapid and robust analytical technique would address these deficiencies. Mass spectrometry (MS) is a standard analytical technique known for its specificity and accuracy. New advancements in research and technology have produced the ability to miniaturize MS while retaining its superior capabilities in identification. The characteristics of IGSR also pose issues in terms of validity, such as specificity to discharging a weapon, and ability to be transferred or wiped off. Qualities such as these can lead to both false negatives and false positives. In recent years, advances in forensic science research have studied the composition of organic gunshot residue (OGSR) as well as new methods for detecting these compounds. Research has pointed towards advantages in OGSR that would rectify the analytical issues seen in using IGSR as the target compound. Some qualities of OGSR that would improve GSR detection are its specificity to GSR, the molecular complexity of its components, its higher persistence on surfaces, and lower transferability. This study addressed both issues by employing the MX908 High Pressure Mass Spectrometer and developing an analytical method for major OGSR targets. The objective of this research was to test the MX908’s ability to ionize and detect Nitroglycerin (NG), Diphenylamine (DPA), Ethyl Centralite (EC), Dibutyl Phthalate (DBP), and Nitroguanidine (NQ). Furthermore, these experiments tested a range of voltage parameters to achieve optimal fragmentation, and ultimately an accurate and specific analytical method.

Improvised explosives may be based on smokeless gunpowder, fertilizers, or inorganic oxidizers such as nitrate (NO3-), chlorate (ClO3-), and perchlorate (ClO4-) salts. Identification is a priority for the military and law enforcement but due to their varying physical properties and complexity, identification can be challenging. Consequently, three methods have been developed to aid in presumptive and confirmatory detection. Smokeless powder contains plasticizers, stabilizers, dyes, opacifiers, flash suppressants, and other compounds. Identification of these additives can narrow down or identify the brands of smokeless powder used in a device. Fourteen organic smokeless powder components were identified by capillary electrochromatography (CEC) using a hexyl acrylate monolithic stationary phase coupled to UV detection and time-of-flight mass spectrometry (TOF-MS). The CEC-UV method efficiently detects all 14 organic components, while TOF-MS provides sensitivity and selectivity. A mixed smokeless powder component standard was analyzed and the composition of the additive package in commercial smokeless powders determined. Detection limits ranged from 1.0 – 3.2 μg/ml and analysis time was 18 minutes. Second, a procedure for the detection of urea nitrate (UN) and ammonium nitrate (AN) by infusion electrospray ionization - mass spectrometry (ESI-MS/MS) was developed. Solubility tests were performed to find a solvent for both UN and AN that did not cause UN to dissociate. Two adduct ions were detected for each explosive: for AN, m/z 178 [2AN+NH4]+ and m/z 258 [3AN+NH4]+ ions, and for UN m/z 185 [UN+NO3]− and m/z 248 [UN+HNO3+NO3]−. Specificity of the analysis was examined by mixing the explosives with various salts and interferents. Gas-phase adduct ions were useful in distinguishing between ion pairs and mixed salts. Finally, a paper microfluidic device (PMD) was developed as a presumptive test using colorimetric reagents for the detection of ions associated with improvised explosives. The device was configured to test for nitrate (NO3-), nitrite (NO2-), chlorate (ClO3-), perchlorate (ClO4-), and urea nitrate (UN). Proof of concept was performed using extracts of soil containing inorganic oxidizers. The development of these analytical methods allows the detection of smokeless powder components, fertilizers, and oxidizers and expands the suite of analytical methods available for the analysis of improvised explosives.

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.