Indiana University-Purdue University Indianapolis (IUPUI) / In Headspace Solid-Phase Microextraction (Headspace SPME), a sample is heated to encourage a portion of the analyte into the headspace of a vial. A coated fiber is introduced into the sample headspace and the analyte is adsorbed onto the fiber coating. Total Vaporization Solid-Phase Microextraction (TV-SPME) is a technique that is derived from this technique. In TV-SPME, liquid samples are completely vaporized allowing for better adsorption and fewer matrix effects. This method does not require any sample preparation, utilizes minimal supplies and can be automated, making it both an efficient and cost-effective method. Chapter 1 will discuss the theory of SPME and TV-SPME. In Chapter 2, the detection of ɣ-hydroxybutyric acid (GHB) and ɣ-butyrolactone (GBL) in beverages is discussed. The detection of these compounds in beverages is of importance because these drugs may be used to facilitate sexual assault. This crime utilizes substances that cause sedation and memory loss. The derivatization of GHB as well as the properties that make GHB difficult to detect will be discussed. Chapter 3 will discuss the detection of methamphetamine and amphetamine (as their trifluoroacetyl derivatives), GBL, and the trimethylsilyl derivative of GHB in human urine. Amphetamine is a metabolite of methamphetamine, therefore, both drugs should be identified within biological samples. GHB and GBL are metabolites of one another and interconvert when in aqueous solution. This interconversion will be discussed. Chapter 4 will cover method optimization of the Total Vaporization Solid-Phase Microextraction method. Analytes of interest for these analyses were methamphetamine, amphetamine, GHB, and GBL. The optimal extraction temperature ranging from 60-160°C of each drug will be discussed as well as why higher temperatures may not be suitable for this method. A limit of detection study for methamphetamine and amphetamine will also be covered. Chapter 5, the future work chapter, will discuss future analyses using the Total Vaporization Solid-Phase Microextraction method including the analysis of powder materials, plant material, and toxicological samples. Powder material will include the analysis of individual powdered drugs as well as realistic drug mixtures. Some analyses on individual powder samples has already been completed and will be shown. Plant material will include the analysis of naturally occurring compounds found in marijuana plants as well as synthetic cannabinoids. Toxicological samples will expand on previously mentioned urine samples to include drugs such as benzoylecgonine and THC-COOH.

Tracer gas surveys are a powerful means of assessing air quantity in underground mine ventilation circuits.  The execution of a tracer gas style ventilation survey allows for the direct measurement of air quantity in locations where this information is otherwise unattainable.  Such instances include inaccessible regions of the mine or locations of irregular flow.  However, this method of completing a mine ventilation survey is an underused tool in the industry.  This is largely due to the amount of training required to analyze survey results. As well, the survey is relatively slow because of the time required to perform analysis of results and the time required to allow for the total elution of tracer compounds from the ventilation circuit before subsequent tracer releases can be made.  These limitations can be mitigated with the development of a protocol for a novel tracer gas which can be readily implemented with existing technology.  Enhanced tracer gas techniques will significantly improve the flexibility of ventilation surveys.  The most powerful means to improve tracer gas techniques applied to mine ventilation surveys is to alter existing protocols into a method that can be readily applied where tracer surveys already take place. One effective method of enhancing existing tracer gas survey protocols is to simply add a second tracer gas that can be detected on a gas chromatograph -- electron capture detector (GC-ECD) using the same method as with the existing industry standard tracer, sulfur hexafluoride (SF6).  Novel tracer gases that have been successfully implemented in the past called for complex analysis methods requiring special equipment, or were designed for inactive workings.  Experimentation with perfluoromethylcyclohexane (PMCH) and SF6 allowed for ideal chromatographic results.  PMCH is a favorable selection for a novel tracer to work in tandem with SF6 due to its chemical stability, similar physical properties and detection limits to SF6, and its ability to be applied and integrated into an existing system.  Additionally, PMCH has been successfully utilized in other large-scale tracer gas studies. Introduction of a novel tracer gas will make great strides in improving the versatility of underground tracer gas ventilation surveys, but further improvement to the tracer gas technique can be made in simplifying individual steps.  One such step which would benefit from improvement is in sampling.  Solid phase microextraction (SPME) is a sampling method that is designed for rapid sampling at low concentrations which provides precise results with minimal training.  A SPME extracting phase ideal for trace analysis of mine gases was selected and a GC-ECD protocol was established.  The protocol for fiber selection and method optimization when performing trace analysis with SPME is described in detail in this thesis.  Furthermore, the impact of sampling with SPME under varying turbulent conditions is explored, and the ability of SPME to sample multiple trace analytes simultaneously is observed. / Master of Science

No description available.

No description available.

No description available.

No description available.

No description available.

Preventing flavor fade requires an understanding of the relationship between carbonyl amine and lipid oxidation reactions. The polyunsaturated fatty acid content of lipids in peanuts makes them more susceptible to lipid oxidation. The major by-products of the oxidation reaction are nonanal, hexanal, octanal, and decanal. These chemicals are associated with cardboardy, painty, and oxidized flavors associated with flavor fade. The carbonyl-amine reaction yields a variety of pyrazines with positive flavor attributes. Initial flavor notes were explored through sensory work, Gas Chromatography-Olfactometry, and chemical analysis. The fresh roasted volatiles produced from roasted peanuts and the aldehydes resulting from oxidation were also evaluated using GC-FID to quantify and identify the pyrazines and hexanal over a 21 day storage period. Electronic Nose was used to determine differences between storage periods. Gas chromatography-Olfactometry identified potent pyrazines contributing to fresh roasted peanutty aroma in fresh peanuts. Using GC-FID a significant decrease (p<.05) in 2-ethylpyrazine and 2,3-diethylpyrazine concentration was found over a 21-day period. No significant difference (p>0.05) was noted in the other pyrazines evaluated. A significant increase (p<0.05) was noted in the hexanal concentration over a 21-day period. The peroxide values and sensory analysis correlated directly with the GC-FID results with a significant increase (p<0.05) in peroxide value at Day 14 and Day 21, and a significant decrease (p<0.05) in fresh roasted peanuty flavor from days 0-21 and a significant increase (p<.05) in painty, cardboardy and bitter from days 7-21. The electronic nose successfully separated Day 0 and Day 21 samples from Day 7 and 14, which were also separated, but with minimal overlap. / Ph. D.

The effect of wine matrix ingredients and conditions on the headspace (HS) sampling of 3-alkyl-2-methoxypyrazines was investigated with solid-phase microextraction (SPME) and capillary gas chromatography, using a nitrogen phosphorus detector. Changes in the recovery of 3-ethyl-, isopropyl-, sec-butyl-, and isobutyl-2-methoxypyrazines from the static headspace of synthetic wine matrices spiked with 5mg/L of each analyte were investigated and reported as a function of SPME fiber type, extraction time, and temperature. The influence of pH, ethanol, phenolics, and ground oak was studied. DVB/Carboxen?/PDMS SPME fibers at an extraction temperature of 50°C for 30 minutes with 30% (w/v) added sodium chloride resulted in the highest analyte recoveries. Although, PDMS (100 micron) SPME fibers at an extraction temperature of 35°C for 30 minutes with 30% (w/v) added sodium chloride resulted in the lower analyte recoveries, the fiber remained functional after 50 to 75 analyses after other coatings deteriorated. Changing the sample ethanol concentration from 0 to 20% (v/v) resulted in an exponential decrease in the recovered analytes. Below pH 2, there was extensive loss of the analytes in the headspace. No measurable impact on alkylmethoxypyrazine headspace concentrations was observed with exposures to selected phenolics and to ground oak. / Master of Science

No description available.