Biofuels are of particular interest as they have the potential to reduce our dependence on petroleum-derived fuels for transportation. 1-Hexanol is a promising renewable long chain alcohol that can be used in conventional fuel blends or as a cosolvent for biodiesel mixtures. However, the fundamental combustion properties of 1-hexanol have not been fully characterized in the literature. Thus, new experimental results, consisting of temperature and concentration profiles of stable species were obtained for the oxidation of 1-hexanol generated in an opposed-flow diffusion flame at 0.101 MPa. The kinetic model consists of 361 chemical species and 2687 chemical reactions (most of them reversible). This experimental data were compared to the predicted values of a detailed chemical kinetic model proposed in literature to study the combustion of 1-hexanol. Reaction pathway and sensitivity analyses were performed to interpret the results. In addition, several improvements were investigated to optimize the proposed chemical kinetic mechanism.

Chemical modeling has become an important subject of research in applied thermodynamics for designing, developing, optimizing and controlling of different industrial processes. In this work, a new database for successful modeling of solid-aqueous phase equilibria in specific hydrometallurgical processes was developed using the Mixed Solvent Electrolyte (MSE(H3O+)) model of the OLI Systems software. The ionic interaction parameters between dominant species in the solution were determined by fitting available binary and ternary experimental data such as mean activity, heat capacity and solubility data; then they were validated in multi-component systems. Developed model predicted the phase behaviour in ammoniacal solutions containing cobalt, nickel, copper, and zinc in the Copper Boil process. New sets of double-salt solubility data were measured and used for accuracy validation of the model. Using HSC 6.1 software linked with MSE model, the copper boil processes was simulated successfully to provide some practical recommendations for the optimum process operation.

A critical concern in metabolic engineering is the need to balance the demand and supply of redox intermediates. Bioelectrochemical techniques offer a promising method to alleviate redox imbalances during the synthesis of biochemicals. Broadly, these techniques reduce intracellular NAD+ to NADH and therefore manipulate the cell’s redox balance. The cellular response to such redox changes and the additional reducing can be harnessed to produce desired metabolites. In the context of microbial fermentation, these bioelectrochemical techniques can improve product yields and/or productivity. We have developed a method to characterize the role of bioelectrosynthesis in chemical production using the genome-scale metabolic model of E. coli. The results elucidate the role of bioelectrosynthesis and its impact on biomass growth, cellular ATP yields and biochemical production. The results also suggest that strain design strategies can change for fermentation processes that employ microbial electrosynthesis and suggest that dynamic operating strategies lead to maximizing productivity.

Little is known about the enzyme-substrate interactions occurring during the dechlorination of chloroform (CF) and 1,1,1-trichloroethane (1,1,1-TCA) by the enrichment culture containing Dehalobacters, hereafter called DHB-CF/MEL. Compound specific isotope analysis (CSIA) is used to investigate the factors which may affect the isotope fractionation observed for CF and 1,1,1-TCA dechlorination. This thesis reports the first isotope enrichment factors observed for CF biodegradation at -27.5‰ ± 0.9‰, thus providing fundamental information for comparing isotope enrichment factors observed during trichlorinated alkane degradation by DHB-CF/MEL. The thesis also reports how the presence of CF and 1,1,1-TCA influences isotope fractionation and explores the possible influence of substrate inhibition on isotope fractionation during 1,1,1-TCA dechlorination. The data suggests that substrate inhibition during 1,1,1-TCA dechlorination by DHB-CF/MEL may not affect carbon isotope fractionation. The results suggest that CSIA is a promising monitoring tool even for the simultaneous biodegradation of CF and 1,1,1-TCA at different 1,1,1-TCA starting concentration.

Treatment of vision impairing diseases involves drug transport through the vitreous humor. Diffusion cells were used to measure macro-scale (mutual) diffusivity (Dm) to understand how solute size affects diffusion through the vitreous humor of rabbit and porcine eyes. Solutes examined included timolol maleate, dexamethasone sodium phosphate (DMSP), sodium fluorescein, and FITC-dextrans (4, 40, and 150kDa). Diffusivity was inversely dependent on solute size. The Dm's of small solutes in the vitreous were 30 – 65% of that in PBS, while the Dm's of large solutes were 40 – 60% of that in PBS. Extrapolations to the human eye produced similar results using diffusivities based on either species. We used Diffusion Ordered NMR Spectroscopy to measure micro-scale (self) diffusivity (Ds) of DMSP through vitreous humor. The Ds and Dm were significantly different in PBS, but similar in vitreous. A method for obtaining in vivo imagery and data of vitreous fluorophore distribution is also presented.

In recent years, uranium pollution in the environment has been recognized as a serious threat, and novel in situ microbial bioremediation strategies have been incorporated into field-scale contaminated sites. The Oak Ridge Integrated Field-scale Subsurface Research Challenge (IFC) site is one of the largest uranium contaminated areas in the United States, and a literature review has revealed the potential of uranium reduction by dominant Anaeromyxobacter dehalogenans species that respire during bioremediation. A genome-scale model of A. dehalogenans, a unique microbe with diverse metabolic capabilities that thrives in the natural environment, has been developed, and applied to an in silico field-scale computational setting for evaluation of the biotic uranium reduction in the Oak Ridge IFC site. The metabolic model of A. dehalogenans was integrated into an expanded microbial community framework for the prediction of chemical profiles, and subsequent scenario evaluation of in situ measured data.

The pulp and paper industry has been struggling to meet the new and stringent TRS (Total Reduced Sulphur) emission compliance standards established in recent years. However, a new approach by some regulatory bodies gives intricate operational parameters a new and important role in achieving environmental compliance. TRS compounds that cause the distinctive pulp mill odour, originate from sodium sulphide in white liquor used in the kraft pulping process. Up to 20% of TRS emissions could originate from the lime kiln and lime mud solids content is one of the operational parameters that could help reduce the TRS emissions from the lime kiln. Residual sodium sulphide in the lime mud that results in TRS gases, is dissolved in the moisture content of the mud. Although efficient lime mud washing can remove most of the residual sodium sulphide, the remaining moisture content of the mud still contains some sodium sulphide. Therefore, improved lime mud dewatering can be effective in reducing the TRS emissions from the lime kiln. Data presented in this study confirms that as the lime mud solids content increases, TRS emissions from the lime kiln decrease. Data analysis demonstrates a negative linear correlation at 5% significance level between TRS emissions and lime mud solids.

In this work the methodology is developed to study spreading and penetration of a custom ink-jet ink formulation, containing hydrophobic cationic crystal violet dye, ethoxylated surfactant, and ink solvent marked by lithium salt. With a new technique utilizing Time-of-Flight Secondary Ion Mass Spectrometry imaging, the ink component distribution and its effect on print quality of uncoated and coated papers are evaluated. High spatially resolved images obtained by ToF-SIMS illustrate differentiation of individual ink components, with ink solvent spreading more than the dye in all paper samples. Uncoated papers show greater and more irregular spreading leading to poor edge definition and poor print quality. Large separation of the dye from the solvent in the vertical direction of multipurpose and photo glossy ink-jet paper suggests a step-wise progression of ink penetration: ink flows through a more porous structure in the x-direction before advancing to the next sublayer in the z-direction of paper.

The overall objective of this research is to identify and optimize enzymatic applications that have the potential to degrade middle lamella lignin, so as to decrease economic and environmental costs associated with the production of mechanical pulp. Non-productive binding of enzyme to lignin in lignocellulosic biomass reduces enzyme availability and efficiency. The elucidation of non-productive binding behavior between hydrolytic enzymes and lignocellulosic substrates could significantly improve the efficiency of corresponding industrial bioprocesses. The first part of this report presents a study that characterizes non-catalytic interactions between enzymes and fibre. The second part of this report presents the biochemical and mutational studies of a novel, small laccase SCO6712 from Streptomyces coelicolor. The findings from this research support the design, control, and optimization of enzymatic treatments of lignocellulosic fibres in the pulp and biofuel industries.

A hygroexpansimeter, cockling tester and a novel x-ray microtomography technique were employed to characterize hygroexpansivity as well as macro- and micro-scale cockling of wood-free paper sheets containing varying amounts of aspen high yield pulp (HYP) in order to validate its potential applicability in inkjet printing. Results from the hygroexpansimeter confirm previous findings that substitution levels of 30% and above lead to a slight deterioration of hygroexpansivity; however, contrary to the expected outcome, aspen HYP did not necessarily result in a higher tendency to form cockles. In fact, a comparison of the cockling behaviour between various paper samples and commercial paper substantiates that up to 40% of aspen HYP can replace hardwood bleached Kraft pulp. The preservation of out-of-plane dimensional stability in non-coated samples is most likely due to the increase in bending stiffness of the paper as it became bulkier with more aspen HYP.