This research focused on the use of nanoscale zero-valent iron (NZVI) to remediate trinitrotoluene (TNT). Zero-valent iron has demonstrated effective degradation of TNT, however, these particles themselves have significant problems in treating sorbed phase TNT in the aerobic environment. This research was comprised of four areas: degradation studies of neat nano-iron with aqueous TNT, degradation studies of nanoiron emulsion with aqueous TNT, characterization of TNT in Vieques, Puerto Rico sediment, and Solid Phase Microextraction (SPME) technique interface with HPLC. Both neat and emulsion NZVI studies showed TNT degradation. More degradation was seen in studies using fresher iron. The results from our characterization study in Vieques, PR showed no presence of TNT within our detection limits of 0.0625ppm. Also, SPME is a new extraction solvent saving technique being explored because of its reproducible extractions in water. This work also gives a brief history of SPME and possible uses with TNT.

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<p dir="ltr">Gas chromatography-mass spectrometry (GC-MS) is a frequently used technique in forensic chemistry for the identification of controlled substances and explosives. GC-MS can be coupled with solid-phase microextraction (SPME), in which a fiber with a sorptive coating is placed into the headspace above a sample or directly immersed in a liquid sample. Analytes are adsorbed onto the fiber which is then placed inside the heated GC inlet for desorption.</p><p dir="ltr">Illicit drugs are often found in the form of impure solids, mixed with other drugs, adulterants, and diluents. A simple method for the quick identification of drugs including methamphetamine, cocaine, heroin, fentanyl, and pharmaceutical tablets was developed. Headspace SPME methods were utilized with an elevated extraction temperature for the detection of various drugs in powder and tablet form. An extraction temperature of 120°C was used to encourage analytes into the headspace of the vial. A sample of the solid drug was placed in a headspace vial with no prior sample preparation or clean-up. This vial was then heated inside of an agitator where the sample was extracted. It was found that drugs in solid and tablet form can be detected using this high temperature headspace SPME method at the temperature of 120°C with no prior sample preparation. This method is simple, efficient, and cost effective for the detection of legal and illicit drugs in solid form.</p><p dir="ltr">Headspace SPME may also be used for the analysis of explosive materials. Canines trained at detecting hidden explosives should be trained using real explosive materials that have minimal contamination by other explosive odors to ensure accurate identification of potential threats. Therefore, the potential for cross-contamination between training aids is of importance. There are various storage methods in use by canine handlers such as plastic and cloth bags, but these can lead to cross-contamination between training aids during storage. Alternatively, odor-permeable membrane devices (OPMDs) may store training aides and be used as a delivery device. A membrane in the OPMD allows for volatile compounds from the training aids to be released during training while helping to prevent contaminants from entering the device. OPMDs were used in addition to traditional storage containers to monitor the contamination and degradation of 14 explosives used as canine training aids. Samples included explosives that contain highly volatile compounds like dynamite and explosives with less volatile compounds like RDX. Explosives were stored individually using traditional storage bags or inside of an OPMD at two locations, IUPUI and an Indianapolis Metropolitan Police Department. The police department actively used the training aids during canine trainings. Samples from each storage type at both locations were collected at 0, 3, 6, and 9 months and analyzed using Fourier transform infrared (FTIR) spectroscopy and GC-MS with SPME. FTIR analyses showed no signs of degradation of the training aids from any timepoint or location. GC-MS identified cross-contamination from ethylene glycol dinitrate and/or 2,3-dimethyl-2,3-dinitrobutane across almost all samples regardless of storage condition. The contamination was found to be higher among training aids that were stored in traditional ways and were in active use by canine teams. Additionally, Time 0 had the highest level of contamination, indicating that explosive training aids are received from the vendors with initial cross-contamination.</p><p dir="ltr">To test the initial cross-contamination levels of training aids, 11 explosive materials were ordered from three different vendors. A 1-gram sample of each was collected and analyzed using SPME with GC-MS. In several cases, explosive materials that are commercially available already exhibit elevated levels of contamination. This indicates that training aids must be acquiring contamination during manufacturing and/or storage at the vendor facility. The cross-contamination of explosive canine training aids stored in OPMDs was further evaluated and compared to traditional storage methods. This was done by storing various combinations of storage containers such as cloth bags, velcro bags, and OPMDs along with explosives and using activated charcoal strips to collect the volatile compounds such as 2,3-dimethyl-2,3-dinitrobutane and ethylene glycol dinitrate. Only one type of storage container, a velcro bag, showed evidence of contamination, indicating that OPMDs may not further prevent cross-contamination of explosive training aids.</p>

Indiana University-Purdue University Indianapolis (IUPUI) / Canines can detect different diseases simply by smelling different biological sample types, including urine, breath and sweat. This has led researchers to try and discovery unique volatile organic compound (VOC) biomarkers. The power of VOC biomarkers lies in the fact that one day they may be able to be utilized for noninvasive, rapid and accurate diagnostics at a point of care using miniaturized biosensors. However, the identity of the specific VOC biomarkers must be demonstrated before designing and fabricating sensing systems. Through an extensive series of experiments, VOCs in urine are profiled by solid phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) to identify biomarkers for breast cancer using murine models. The results from these experiments indicated that unique classes of urinary VOCs, primarily terpene/terpenoids and carbonyls, are potential biomarkers of breast cancer. Through implementing chemometric approaches, unique panels of VOCs were identified for breast cancer detection, identifying tumor location, determining the efficacy of dopaminergic antitumor treatments, and tracking cancer progression. Other diseases, including COVID-19 and hypoglycemia (low blood sugar) were also probed to identify volatile biomarkers present in breath samples. VOC biomarker identification is an important step toward developing portable gas sensors, but another hurdle that exists is that current sensors lack selectivity toward specific VOCs of interest. Furthermore, testing sensors for sensitivity and selectivity is an extensive process as VOCs must be tested individually because the sensors do not have modes of chromatographic separation or compound identification. Another set of experiments is presented to demonstrate that SPME fibers can be coated with materials, used to extract standard solutions of VOCs, and analyzed by GC-MS to determine the performance of various gas sensing layers. In the first of these experiments, polyetherimide (PEI) was coated onto a SPME fiber and compared to commercial polyacrylate (PAA) fibers. The second experiment tuned the extraction efficiency of polyvinylidene fluoride (PVDF) - carbon black (CB) composites and showed that they had higher sensitivity for urinary VOC extraction relative to a polydimethylsiloxane (PDMS) SPME fiber. These results demonstrate SPME GC-MS can rapidly characterize and tune the VOC adsorption capabilities of gas sensing layers.

Measuring lipid oxidation is useful as a means of monitoring oxidative stress, such as that induced by clinical conditions or environmental exposure. Characteristic volatile compounds, often with low threshold odors, are secondary products of lipid oxidation reactions. Metallic flavor in food and beverages has been linked with oxidation of lipids in the oral cavity. Breath, an emerging medium for analysis of internal condition, is one means of measuring the metal-induced lipid oxidation responsible for this flavor. This project analyzes the breath of human subjects, as well as lipid oxidation of in vitro samples to identify compounds responsible for producing metallic flavor, which result from the oxidation of lipids in the oral cavity. Because these analytes are found at extremely low (picomolar to nanomolar) concentrations, preconcentration of samples prior to gas chromatography-mass spectrometry analysis is crucial. This study utilizes both solid phase microextraction (SPME) and micromachined silicon micropreconcentrators to concentrate compounds in breath to optimize analysis. / Master of Science