EVOLUTION OF SELECTED ISOPRENE OXIDATION PRODUCTS IN DARK AQUEOUS AMMONIUM SULFATE

The aqueous phase processing of glyoxylic acid, pyruvic acid, oxalic acid and methylglyoxal was studied simulating dark and radical free atmospheric aqueous aerosol. A novel observation of the cleavage of a carbon-carbon bond in pyruvic acid and glyoxylic acid leading to their decarboxylation was made in the presence of ammonium salts but no decarboxylation was observed from oxalic acid. The empirical rate constants for decarboxylation were determined. The structure of the acid, ionic environment of solution and concentration of species found to affect the decarboxylation process. A tentative set of reaction mechanisms was proposed involving nucleophilic attack by ammonia on the carbonyl carbon leading to fragmentation of the carbon-carbon bond between the carbonyl and carboxyl carbons. Whereas, the formation of high molecular weight organic species was observed in the case of methylglyoxal. The elemental compositions of the species were determined. It was concluded that, additional pathways that are not currently known likely contribute to aqueous phase processing leading to high molecular weight organic species. Under similar conditions in atmospheric aerosol, the aqueous phase processing will markedly impact the physicochemical properties of aerosol.

DEVELOPMENT OF A 2-DIMENSIONAL FINITE VOLUME MODEL TO ASSESS HYDRODYNAMIC AND MICROBIAL CONTROLS ON DNAPL DISSOLUTION AND DETOXIFICATION

Tetrachloroethene (PCE) and trichloroethene (TCE) form dense non-aqueous phase liquids (DNAPLs), which are persistent groundwater contaminants. DNAPL dissolution can be "bioenhanced" via dissolved contaminant biodegradation at the DNAPL-water interface. This research hypothesized that: (1) competitive interactions between different dehalorespiring strains can significantly impact the bioenhancement effect, and extent of PCE dechlorination; and (2) hydrodynamics will affect the outcome of competition and the potential for bioenhancement and detoxification. A two-dimensional coupled flowtransport model was developed, with a DNAPL pool source and multiple microbial species. In the scenario presented, Dehalococcoides mccartyi 195 competes with Desulfuromonas michiganensis for the electron acceptors PCE and TCE. Simulations under biostimulation and low velocity (vx) conditions suggest that the bioenhancement with Dsm. michiganensis alone was modestly increased by Dhc. mccartyi 195. However, the presence of Dhc. mccartyi 195 enhanced the extent of PCE transformation. Hydrodynamic conditions impacted the results by changing the dominant population under low and high vx conditions.

MAGNETO-PHOTONIC CRYSTALS FOR OPTICAL SENSING APPLICATIONS

Among the optical structures investigated for optical sensing purpose, a significant amount of research has been conducted on photonic crystal based sensors. A particular advantage of photonic crystal based sensors is that they show superior sensitivity for ultra-small volume sensing. In this study we investigate polarization changes in response to the changes in the cover index of magneto-optic active photonic band gap structures. One-dimensional photonic-band gap structures fabricated on iron garnet materials yield large polarization rotations at the band gap edges. The enhanced polarization effects serve as an excellent tool for chemical sensing showing high degree of sensitivity for photonic crystal cover refractive index changes. The one dimensional waveguide photonic crystals are fabricated on single-layer bismuth-substituted rare earth iron garnet films ((Bi, Y, Lu)3(Fe, Ga)5O12 ) grown by liquid phase epitaxy on gadolinium gallium garnet substrates. Band gaps have been observed where Bragg scattering conditions links forward-going fundamental waveguide modes to backscattered high-order waveguide modes. Large near-band-edge polarization rotations which increase progressively with backscattered-mode order have been experimentally demonstrated for multiple samples with different composition, film thickness and fabrication parameters. Experimental findings are supported by theoretical analysis of Bloch modes polarization states showing that large near stop-band edge rotations are induced by the magneto-photonic crystal. Theoretical and experimental analysis conducted on polarization rotation sensitivity to waveguide photonic crystal cover refractive index changes shows a monotonic enhancement of the rotation with cover index. The sensor is further developed for selective chemical sensing by employing Polypyrrole as the photonic crystal cover layer. Polypyrrole is one of the extensively studied conducting polymers for selective analyte detection. Successful detection of aqueous ammonia and methanol has been achieved with Polypyrrole deposited magneto-photonic crystals.