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Essential oils are natural products used to flavor food and beverages. With the increase in nutrition conscious consumers, manufacturers of food additives and food products are faced with the challenge of making healthy alternatives. In particular, food products going to market with label claims stating reductions in sugar and salt, organic certified, organic compliant, and all natural; moreover the ingredients used in flavors must meet these label claims as well. More often than not, the challenge in using ingredients that follow these requirements is the pricing, the sourcing and the variability among those sources. Variability is common in the ingredients coming from nature such as fruits and plants because the area of cultivation can vary by the soil at the sight of planting and/or the climate in the region. Pricing is also problematic in naturally grown ingredients because it is a matter of supply and demand. Stock could be depleted from natural disasters, disease carrying pest(s), pests that consume the crop, and/or other causes for scarce supply of crop(s). Essential oils are natural byproducts of fruit, peels, and leaves from plants that contribute to flavor formulae for a large variety of food products. Because the essential oils are a crop based commodity, every variety has inherent differences based on the growing conditions and their ripening stages [1]. Nevertheless, each type of oil has marker chemicals that make up the majority of its composition; these marker chemicals have the tendency to degrade over time based on their interaction with light, oxygen exposure, and temperature. For companies that manufacture flavorings, understanding the variability among sources of essential oils as well as the possible degradants of essential oils is valuable information to obtain because it is possible the variants and degradants will negatively impact the flavor profile. Flavor is without question the most important attribute of the food we consume and by default stability of said flavor(s) need to be understood [30]. The content in this dissertation involves the stability analysis of a common essential oil, Oil Mandarin Italian Select, from Citrus Reticulata Blanco. It has known off notes that form from unknown causes. Most common is the plastic note that has formed in carbonated products like soda. Studying this particular essential oil in various conditions is intended to shed light on what those degradants are and under which conditions they form to give mandarin oil an off-note when applied to high acid and carbonated beverage applications. Once the note is reproduced, a correlation between analytical data and sensory interpretation of the oil will be developed. Mandarin essential oil being in the Citrus genus is traditionally analyzed via gas chromatography (GC) because of the high quantities of volatile constituents that give an oil high aroma activity. The volatile fraction of mandarin oil to be studied includes stability of methyl-N-methylanthranilate (MNMA), a major component giving mandarin its distinct grapey character, as well as gamma terpinene, thymol, sinensal, alpha pinene, beta pinene, myrcene, para cymene, alpha terpineol, and beta caryophyllene. Each of these ten compounds contributes to the unique flavor profile of mandarin oils when compared to orange and tangerine essential oils [1]. It was the common knowledge that para cymene can be perceived as rancid in aroma and the many interconversions the terpenes make that cause para cymene formation in Citrus oils, which made monitoring the changes of this chemical in the three stability environments crucial. Attention is being paid to para-cymene, as a specific marker of degradation in Citrus. The data obtained from the applied stability studies were challenging to understand as the marker chemicals are volatile and sensitive to chemical change. In this work the chemical changes and trends were analyzed under various storage conditions. Significant statistical analyses were employed to help define criteria of usability. The analyses were required because of natural variants and apparent inconsistencies of the data. Dixon Q Test and the Z Test were applied to determine outliers. Additionally, the Bland Altman method was applied to compare storage conditions and to determine if this statistical approach could be used to define significant changes in the marker chemical stability. The Bland Altman plots suggest that each component met the statistical limits of agreement, meaning the samplings were not significantly changing, statistically speaking. A final approach to assess the analytical data of the mandarin oil for significant change was the mass balance of each marker chemical from week 0 to week 24. Instrumental fluctuations have an acceptable range of +/- 20% in the industry; hence, a significant change criterion for a chemical in the mass balance must be one that exceeded +/- 20%. Unlike classical statistic methods, the mass balance was indicative that significant change had occurred to the compounds in the three studies. Upon sensory analysis of the oil samples, display of plastic note, oxidation, and overall loss of characteristic mandarin notes, the mass balance was found to correlate best to the significant change detected by sensory evaluation of the oil samplings. Due to the inadequate number of validated methods on Citrus essential oil research and the absence of large groupings of terpenes validated in a unified methodology, reconciliation of mass balance is an underutilized method of assessment in the literature. As a final assessment of the GC method validated, a product containing the selected mandarin oil was analyzed to evaluate the ability of the method to separate the oil components within a significantly more complicated matrix than the initial samples. The method was successful though not all marker chemicals were detected due to their low formulation concentration being below the level of detection of the method. This should not be seen as a failure of the method. For the major components of the essential oil studied, the method was quantitatively successful, meeting industry requirements. / Chemistry

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.

Wood pulp mill effluents continue to attract much attention due to environmental consequences. However, in comparison, very little work has been published on wood pulp extracts themselves. In this investigation, chemithermomechanical (CTMP) pulps as well as Kraft (BKP) pulps were Soxhlet extracted with solvents of different polarity. These two types of pulp extracts were then compared qualitatively using GC-FID and GC-MSD as well as quantitatively based on the percent of extractives obtained. For all the pulps studied, the percent extractives of water > ethyl acetate > cyclohexane. The CTMP extracts exhibited many more components as compared to BKP extracts for all the extractions solvents. The presence of trace chlorinated phenolics in the above wood pulp extracts was also addressed utilizing GC-ECD, GC-EIMS and GC-NCIMS. 4-MCG, 4,5-DCG, 4,5,6-TCG, 3,4,5-TCG, 2,4,6- TCP, 2,3,4,6-TeCP, PCP and 6-MCVN were discovered. Due to a lack of knowledge of the complete history of the wood pulps studied, the exact causes for their discoveries are unknown. Attempts were also made to study the feasibility of Supercritical Fluid Extraction of the above mentioned wood pulps due to the difficulties faced with Soxhlet extractions. The percent extractives obtained using SF-CO₂ and cyclohexane were found to be comparable. / Ph. D.

An explosive vapor generator which produces transient "clouds" of explosive vapors for use in the evaluation of commercial explosive vapor detection systems has been developed based on a capillary gas chromatograph. The design of the vapor generator replaces a flame ionization detector on the gas chromatograph with an effluent heater system to provide a cloud of explosive vapor while preventing condensation onto the walls of the capillary column. This vapor source has been successfully used to produce vapors of dinitrotoluene (DNT), trinitrotoluene (TNT), and 1,3,5-trinitro-1,3,5- triazacyclohexane (RDX). The chemical composition of the output was confirmed by both ion mobility spectrometry, and quadrupole mass spectrometry. Adsorptive effects of TNT and RDX were studied in order to optimize the injection parameters, achieving detection limits three orders of magnitude lower than previously reported. The quantitative output of the system was verified using thermal tube desorption gas chromatography. / Ph. D.

Low levels of biogenic amines occur naturally, but high levels (FDA sets 50 ppm of histamine in fish as the maximum allowable level) can lead to scombroid poisoning. Amines in general are difficult to analyze by Gas Chromatography (GC) due to their lack of volatility and their interaction with the GC column, often leading to significant tailing and poor reproducibility. Biogenic amines need to be derivatized before both GC and HPLC analyses. The objective of this research was to develop a relatively fast, reproducible method to derivatize and quantitate biogenic amines in fish at trace levels using GC/FID. The derivatizing reagent used in the experiments was propyl chloroformate, useful for aqueous samples. To confirm the identity of six derivatized biogenic amines GC/MS was used. To our knowledge no reference spectra for these derivatives has been published. It was concluded that best results are obtained using a Cold-On-Column (C.O.C.) inlet with a short column (15 meters), thick film stationary phase (ZB-5, 1.00μm df), and with recommendations to cut 40 cm from the inlet end of the column every 25 injections when using C.O.C. Duplicate samples of Atlantic Salmon were analyzed on days 0, 3, and 5. Levels of histamine were below 50 ppm for days 0 and 3, but day 5 showed average levels of 160 pm (cadaverine), 1000 ppm (histamine), and 350 ppm (tyramine). Good precision of six amine stardards at 50 ppm was shown: heptylamine 5.2%, putrescine 5.6%, cadaverine 5.0%, histamine 9.9%, tyramine 5.1%, and spermidine 6.2% RSD. / Master of Science

The purpose of this investigation was to test the effect of sample size and carrier gas flowrate on the efficiency (relative to an analytical column) of an annular preparative-scale column. The chromatographic system for this investigation consisted of η-methyl-butyrate injections with nitrogen carrier gas and a liquid phase of Craig polyester succinate on Chromosorb W. The analytical column had an inside diameter of 0.061 inches. The preparative-scale column had an outside diameter of 2.075 inches and an inside diameter of 1.050 inches. The operating temperature for both columns was 215 degrees Fahrenheit. A sample size range of 0.1 to 3.0 milliliters was studied on the preparative-scale unit; this corresponded to a 0.2 to 3.6 microliter range on the analytical unit. Carrier gas flowrates of 4305, 8610 and 17,220 milliliters per minute were studied on the preparative-scale unit. This corresponded to flowrates of 5, 10 and 20 milliliters per minute on the analytical unit. Preparative-scale efficiencies of 20.43, 41.95 and 45.34 per cent were obtained at a sample size of 0.1 milliliter. The above efficiencies correspond to flowwates of 4305, 8610 and 17,220 milliliters per minute. As the sample size was increased to 3.0 milliliters the corresponding efficiencies dropped to 7.20, 17.71 and 27.11 per cent respectively. / Master of Science

Gaseous phase is a critical state of matter around us. It mediates between the solid crust on earth and inter-stellar vacuum. Apart from the atmosphere surrounding us where compounds are present, natively, in a gaseous phase, they are also trapped within soil and dissolved in oceanic water. Further, those that are less volatile do enter the gaseous phase at high temperatures. It is this gaseous phase that we inhale every second. It is thus critical that we possess the tools to analyze a mixture of gaseous compounds. One such method is to separate the components in time and then identify, primarily based on the retention times, also known as gas chromatography. This research focuses on the development of gas detectors and their integration, in different styles, primarily for gas chromatography. Utilizing fabrication techniques used in semiconductor industry and exploiting scaling laws we investigate the ability to improve on conventional gas separation and identification techniques. Specifically, we have provided a new spin to the age-old thermal conductivity detector enabling its monolithic integration with a separation column. A reference-less, two-port integration architecture and a one-of-its-kind released resistor on glass are some of its salient features. The operation of this integrated device with a preconcentrator and in a matrix array was investigated. The more unique contribution of this research lies in the innovative discharge ionization detector. An ultra-low power, sensitive, easy to fabricate detector, it requires more investigation for a thorough understanding and will likely mature to replace the thermal conductivity detector, as the detector of choice for universal detection, in time to come. / Ph. D.

Optimization of capillary gas chromatography-Fourier Transform Infrared (GC-FTIR) spectrometry has been accomplished by studying various columns, lightpipe designs, FTIR detectors and spectroscopic parameters. For adequate separation of complex samples the efficiency of WCOT (Wall Coated Open Tubular) fused silica capillary columns was found to be unmatched by packed columns or wide bore glass capillaries. A consequence of using more narrow bore columns, however, is lower sample capacity and less IR detectability. Two 6 cm light pipes and a more narrow 40 cm lightpipe were compared with respect to both optical throughput and eluent band broadening. FTIR spectroscopic parameters such as mirror velocity and number of scans coadded were examined in order to achieve an optimum signal to noise ratio. The complexity of a particular sample has been shown to dictate certain spectroscopic parameters. The sensitivity differences of two liquid-nitrogen cooled FTIR detectors used in the GC-FTIR experiments have been determined with reference to using them with either a long or short lightpipe. The capability of optimized capillary GC-FTIR has been demonstrated in the analysis of model compound mixtures and comp lex petroleum products including test aviation jet fuels. Major attention was given to the detection and identification of aliphatic and aromatic components in the highly complex samples. Computerized library search routines have been used to tentatively identify eluting components by infrared spectral matching to quality vapor phase library file spectra. Gas chromatography-mass spectrometry (GC-MS) data are also included for the same jet fuel samples to directly compare extent of information provided and relative spectroscopic sensitivities. / Master of Science