A method using gas chromatography for the analysis of carbon dioxide, carbon monoxide, and nitric oxide in diesel exhaust was developed. A gas chromatograph containing a liquid phase column in series with a molecular sieve column, each of which eluted into thermal conductivity detectors, was utilized. Activation of the molecular sieve column was achieved by heat-treating and purging with nitric oxide. The chromatograph was calibrated by introducing sample mixtures of known concentration and measuring the responses. The exhaust gases of a diesel engine were analyzed while the engine operated at constant speed and load. Engine speed was kept at 1400 rpm while several different loads were applied. The results of these tests indicated that carbon dioxide, carbon monoxide, and nitric oxide concentrations all increased with load in the load range studied. Carbon monoxide exhibited a greater dependence on load than did the other compounds. Additionally, water was injected into the intake air stream to study its effect on nitric oxide concentration. Nitric oxide levels were reduced by 15% when a water/fuel mass ratio of 0.75 lb/lb was used. / Master of Science

1. The sensitivity obtained even with the free compounds (except morphine) make gas chromatography a good technique for trace analysis of drugs in biological samples. 2. For many of the drugs studied the detector response curves are not linear with sample concentration but the calibration curves are reproducible if care is exercised. This makes quantitative analysis feasible down to 50-100 nanogram levels with proper technique. 3. Long column life is needed for routine analyses. Those columns employed in this work were used continuously for over seven months with no appreciable deterioration. / Master of Science

The analysis of nitrate-ester propellants and explosives has been performed extensively by gas chromatography for the past decade. As capillary GC technology has advanced, new opportunities for the improvement of existing methods have developed. This investigation probes several of these possibilities. The effect on quantitation of: the solvent, the analysis time, and the use of splitless injection were investigated. Precision was shown to be improved by: 1. using a non-volatile solvent (toluene) rather than CH₂Cl₂, 2. using the most time-efficient method that will allow adequate resolution of the components, 3. using splitless injection (0.80 min. splitless time). After these potential improvements of method were investigated, the mechanism employed in splitless injection was investigated. This mechanism is known as the SOLVENT EFFECT. The investigation showed that: 1. non-volatile components required less splitless time to achieve 100% sample transfer to the column; 2. using splitless injection improved precision over split injection; 3. injector liner design had no effect on precision; 4. column overload did not hurt precision, as long as all peaks remain baseline-resolved; 5. the initial column temperature must be below the boiling point of the solvent (how far below did not appear to be very significant); 6. quantitation is improved by using a solvent that is as non-volatile as possible; 7. varying the split ratio after the split vent has reopened (within the range of 20:1 to 500:1) has no effect on resolving peaks that occur extremely close to the solvent peak. / Master of Science

The main objective of this research was to identify the compounds responsible for persistent odors in biosolids during long-term storage using olfactometry measurements and to determine their generation pattern with regard to time of appearance and decline using gas chromatography-mass spectrometry (GC-MS). Another objective of this study was to investigate the effect of various digestion and dewatering techniques on odors and determine if there is a correlation between the peak concentration and time of appearance of short-tem organic sulfur odors and persistent odors. Headspace analysis was used to quantify short-term odor-causing organic sulfur compounds and persistent odors from compounds such as indole, skatole, butyric acid and p-cresol for an incubation period up to 150 days. A unique odor generation pattern was observed for each of the compounds analyzed for all the dewatered cakes tested in this study. Dewatered cake samples were also analyzed to determine their detection threshold by a trained odor panel and the results were consistent with the general pattern of odor generation observed in this study. Positive correlations were observed between the peak concentration of organic sulfur and persistent odor compounds whereas little or no relationship was observed between their times of appearance. The type of sludge used in digestion (primary sludge, WAS and mix) was found to affect the production of odor-causing compounds significantly. Primary sludge produces the highest odors followed by mix. WAS was found to produce biosolids with a low odor concentration. Positive correlation was observed between odor concentration and digestion SRT. Significant reduction in odor concentration was observed when the SRT was increased from 12-days to 25-days. At 45-day SRT, further reduction in odors was not very significant. Moreover, the results from this study indicate that methanogens play an important role in the degradation of both organic sulfur and persistent odors. Although the highest odors during biosolids incubation came from sulfur compounds, the persistent odors must be managed as part of a comprehensive sludge management approach. / Master of Science

The scope of supercritical fluid chromatography continues to enlarge. The use of open tublar and packed columns, nearly universal detectors and the introduction of new mobile phases make it more important. In this work sulfur hexafluoride is evaluated as a mobile phase for supercritical fluid chromatography. The separation of a model aromatic hydrocarbon mixture using different packed columns and operational parameters with UV as a detector is presented. The chromatographic properties of supercritical sulfur hexafluoride and supercritical carbon dioxide are compared under corresponding chromatographic parameters. / Master of Science

A gas chromatographic study was made to quantitatively analyze the effluents produced during the thermal cyclization of several polyimidazopyrrolone (pyrrone) model compounds. The study yielded information on analogous polymeric reactions. The model compounds were programed at 5° C/min from 25° to 400° C and volatile species were purged into a gas chromatograph at 25° intervals. An analysis of the effluents revealed that the cyclization reactions are concerted and generally occur below 250°C. The percent of conversion of the model compounds is readily determined by quantitating those reaction products amenable to gas chromatographic analysis. Only the amide-acid-amine and meta-benzimidazole-acid model compounds exhibited complete conversion to the pyrrone structure. Evidence that decarbo:xylation has occurred in the other compounds is presented. / Master of Science

Separation of complex gaseous mixtures using gas chromatography (GC) is an important step in analytical systems for environmental monitoring, medical diagnosis, and forensic science. Due to its high resolving power, analysis speed, and small sample size, GC, has become the premier technique for separation and analysis of volatile and semi-volatile organic compounds. Miniaturization of analytical systems has become a major trend which is mainly driven by advancements in microfabrication techniques and a need for portable lab-on-a-chip systems for onsite monitoring. Microfabricated columns have been explored for applications in analytical processes like GC in several research studies. These microGC columns typically have open rectangular or open circular cross sections which is a result of the etching process utilized in the fabrication. This work reports the fabrication and performance of a new generation of silicon-on-glass micro-electro-mechanical systems (MEMS) based GC columns with microposts namely "semi-packed." These columns can be fabricated on a 2 cm2-die for a 1 m-long channel or a 1 cm2-die for a 25 cm-long channel. The semi-packed columns have a higher sample capacity as the overall surface area is larger than that of open rectangular columns of the same dimensions. The separation efficiency of these columns is also superior to that of open columns due to the presence of the microposts. As compared to conventional packed columns, the semi-packed columns show lower pressure drops and a more uniform flow profile, both of which contribute to, performance in terms of separation efficiency. / Master of Science

Advances in micro-electro-mechanical-systems (MEMS) along with nanotechnology based methods have enabled the miniaturization of analytical chemistry instrumentation. The broader aim is to provide a portable, low-cost, and low-power platform for the real-time detection and identification of organic compounds in a wide variety of applications. A benchtop gas chromatography (GC) system is considered a gold standard for chemical analysis by analytical chemists. Similarly, miniaturization of key GC components (preconcentrator, separation column, detector, and pumps) using micro- and nanotechnology based techniques is an on-going research field. This dissertation specifically deals with the design, fabrication, coating, and chromatographic testing of microfabricated separation columns for GC. This work can be broadly categorized into three research areas: design and development of new column designs, introduction of new stationary phases and the development of novel fabrication methodologies for integrating functionalized thin-film into microchannels for chromatographic separations. As a part of this research, two high performance new micro column designs namely width-modulated and high-density semi-packed columns are introduced for the first time. Similarly, two new types of functionalized stationary phases are also demonstrated i.e. a highly stable and homogenous silica nanoparticles coating deposited using a layer-by-layer self-assembly scheme and a highly conformal functionalized thin aluminum oxide film deposited using atomic layer deposition. Moreover, novel thin-film patterning methods using different microfabrication technologies are also demonstrated for high-aspect ratio multicapillary and semi-packed columns. / Ph. D.

The use of PAGE of soluble cellular proteins and gas chromatography of cellular fatty acids was studied to determine the possible use of both methods for rapid identification of anaerobic bacteria. Species of <u>Fusobacterium</u> and <u>Capnocytophaga</u> were analyzed to determine the identification accuracy of each system. The electrophoretic patterns of soluble cellular proteins and the cellular fatty acid patterns determined by gas chromatography were found to remain relatively constant within the species examined. This similarity allowed for the development of automated systems using computer programs to analyze the patterns, and compare them to the patterns of known species. Procedures for gas chromatography of cellular fatty acids were developed by Myron Sasser, University of Delaware, and Microbial Identification Systems (Suite 115 Barksdale Professional Center, Newark, Delaware 19711), in cooperation with Hewlett Packard. From this study it was determined that the accuracy of identification of the PAGE analyses was not high, and therefore this method would have limited use in a clinical laboratory. Gas chromatography of cellular fatty acids had a relatively high accuracy, which is still being improved. / Master of Science

With the continued evolution of MEMS-based gas chromatography, the drive to develop new standalone systems with lower power consumptions and higher portability has increased. However, with improvements come tradeoffs, and trying to reduce the pressure drop requirements of previously reported semi-packed columns causes a significant sacrifice in separation efficiency. This thesis covers the techniques for evaluating the separation column in a gas chromatography system as well as the important parameters that have the most effect on a column’s efficiency. Ionic liquids are introduced as a stable and versatile stationary phase for micro separation columns. It then describes a MEMS-based separation column design utilizing density modulation of embedded micro-pillars which attempts to optimize the balance between separation efficiency and pressure drop. / Master of Science / Gas chromatography is a technique used by scientists to separate and identify chemical compounds present in a given test mixture. It is a versatile technique that can be used for qualitative and quantitative analysis of complex mixtures in a variety of applications. However, typical gas chromatography systems are confined to a lab because they are large and consume a lot of power. In order to overcome these problems, different research groups have focused their attention towards the development of portable MEMS-based gas chromatography systems. By miniaturizing the various components of a gas chromatography system, these two main issues can be alleviated. This thesis covers the strategies used to develop and evaluate the separation column of a gas chromatography system and introduce a new MEMS-based column design that will further reduce the power consumption.